Compositions comprising 1,1-difluoroethene (R-1132A)

ABSTRACT

The invention provides a composition comprising 1,1-difluoroethene (R-1132a); a second component selected from the group consisting of hexafluoroethane (R-116), ethane (R-170) and mixtures thereof; and, optionally carbon dioxide (CO 2 , R-744).

This application is a divisional of U.S. patent application Ser. No.14/908,326, which is the U.S. National Phase under 35 U.S.C. § 371 ofInternational Application No. PCT/GB2014/052321, filed Jul. 29, 2014,designating the United States and published in English on Feb. 5, 2015,as WO 2015/015188, which claims priority to United Kingdom ApplicationNo. 1313615.5, filed Jul. 30, 2013, each of which is incorporated byreference in its entirety.

The invention relates to compositions, preferably to heat transfercompositions, and in particular to ultra-low temperature heat transfercompositions which may be suitable as replacements for existingrefrigerants such as R-508A, R-508B, R23 or R13B1.

The listing or discussion of a prior-published document or anybackground in the specification should not necessarily be taken as anacknowledgement that a document or background is part of the state ofthe art or is common general knowledge.

Mechanical refrigeration systems and related heat transfer devices suchas heat pumps and air-conditioning systems are well known. In suchsystems, a refrigerant liquid evaporates at low pressure taking heatfrom the surrounding zone. The resulting vapour is then compressed andpassed to a condenser where it condenses and gives off heat to a secondzone, the condensate being returned through an expansion valve to theevaporator, so completing the cycle. Mechanical energy required forcompressing the vapour and pumping the liquid is provided by, forexample, an electric motor or an internal combustion engine.

Certain refrigerant applications, notably biomedical refrigeration, uselow-boiling refrigerant gases to achieve cooling of materials, typicallyto temperatures of about −85° C. or below. These fluids are sometimesreferred to as ultra-low temperature (ULT) or cryogenic refrigerants.

The most commonly used non-flammable ULT refrigerants currently areR-508A and R-508B. The term R-508 is used herein to refer to R-508A andR-508B, which are both mixtures of trifluoromethane (R-23) withhexafluoroethane (R-116) and are rated A1 by the ASHRAE Standard 34classification.

Typical low-temperature applications of R-508 fluids are normallycascade systems: a first vapour compression refrigeration cycle coolsair inside a refrigerated compartment to between about −80 and −95° C.by evaporation of liquid R-508. The gaseous refrigerant is thencompressed and condensed in a heat exchanger, where it vaporises asecond refrigerant (for example R-404A). A typical condensingtemperature for R-508 in this exchanger is in the range −50 to −30° C.The second refrigerant vapour is compressed by a second compressor andis then condensed against ambient air.

The greenhouse (or global) warming potential (GWP) of low boilingnon-flammable refrigerant gases such as R-508 or R-23 is high (e.g.about 13000), and it is desired to find fluids able to be used in thisapplication with lower GWP, so as to reduce environmental impact ofrefrigerant leakage.

In looking for alternative low temperature refrigerants several otherfactors must also be considered. Firstly, if the fluid is to be used asa retrofit or conversion fluid in existing equipment, or as a “drop-in”to new equipment using an essentially unchanged R-508 system design,then non-flammability is highly desired, as the existing design willhave been based on the use of non-flammable fluid.

If an alternative fluid is to be employed in a wholly new system designthen a degree of flammability may be tolerable; but the use of highlyflammable fluids may impose cost and performance penalties to mitigatehazards. Acceptable charge size (refrigerant mass) in a system is alsogoverned by the flammability classification of the fluid, with class 3fluids, such as ethane, being the most strictly limited. In this case aweaker flammability characteristic is highly desirable since it mayallow larger system charges.

Thirdly, the typical application of such fluids is in commercial orlaboratory based equipment and so the systems will be located inbuildings. It is therefore desirable to have acceptably low toxicity asa characteristic of the fluid.

Furthermore, the volumetric capacity (a measure of the cooling powerachievable by a given size of compressor) and energy efficiency areimportant. This is especially so in cascade operation as inefficiency inthe low temperature stage also increases power consumption of thecompressor in the top stage of the cascade.

R-170 (ethane) has very low GWP, acceptable refrigeration performanceand toxicity but its high flammability limits its application: forexample safety regulations can restrict the maximum charge quantity ofrefrigerant in appliances.

Binary mixtures of R-170 with R-116 have been described by Zhang et al.(J Chem Eng Data 2005 50 2074-2076 and Fluid Phase Equilibria 2006 24073-78). They identified an azeotropic binary composition of these twocomponents.

R-744 (carbon dioxide) is non-flammable but cannot be used alone in thebottom stage of ULT cascade systems because the operating temperaturesare below the triple point of R-744. This means that solid carbondioxide (dry-ice) could form in low pressure sections of the system,leading to blockages, poor control and inefficient operation.

Binary mixtures of R-744 with R-116 have been described by Valtz et al(Fluid Phase Equilibria 258 (2007) 179-185). They identified anazeotropic binary composition of these two components.

R-1132a (1,1-difluoroethene, also known as vinylidene fluoride) also haslow GWP and acceptable toxicity. The flammability of R-1132a is reducedcompared to ethane but it is still in flammability class 2. U.S. Pat.No. 6,054,064 describes the use of R-1132a in certain refrigerantcompositions including mixtures with R-23, R-32, R-125, R-134a andR-143a. The thermodynamic energy efficiency of pure R-1132a is close tothat of R-508 but its refrigeration capacity is reduced.

Thus there is a need to provide alternative refrigerants having improvedproperties such as low GWP, yet possessing acceptable refrigerationperformance, flammability characteristics and toxicology. There is alsoa need to provide alternative refrigerants that may be used in existingdevices such as refrigeration devices with little or no modification.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows phase equilibrium behavior of R-1132/R-116 mixtures showingazeotropy;

FIG. 2 shows vapour pressure of R-1132a/R-116 mixtures;

FIG. 3 shows calculated refrigeration cycle performance forR-1132a/R-116 mixtures;

FIG. 4 shows bubble point pressure of R-170/R-1132a mixtures at −40° C.;

FIG. 5 shows calculated refrigeration cycle performance forR-1132a/R-116/R-744 mixtures; and

FIG. 6 shows flammability for R-744/R-1132a/R-116 at 60° C.

The subject invention addresses the above and other deficiencies by theprovision of a composition comprising 1,1-difluoroethene (R-1132a), asecond component selected from the group consisting of hexafluoroethane(R-116), ethane (R-170) and mixtures thereof and, optionally, carbondioxide (CO₂, R-744). Such compositions, which may be considered to beheat transfer or refrigerant compositions, are referred to hereinafteras compositions of the invention.

Certain compositions of the invention comprise R-1132a and R-116,typically from about 10 to about 99% by weight of R-1132a and from about1 to about 90% by weight of R-116. A preferred such compositioncomprises from about 14 to about 99% by weight of R-1132a and from about1 to about 86% by weight of R-116.

A another preferred composition of the invention comprises from about 35to about 99% by weight of R-1132a and from about 1 to about 65% byweight of R-116. Further preferred compositions of the inventioncomprise from about 36 to about 98% by weight of R-1132a and from about2 to about 64% by weight of R-116, for example from about 36 to about96% by weight of R-1132a and from about 4 to about 64% by weight ofR-116.

A binary minimum-boiling azeotrope has been identified between R-1132aand R-116 by vapour-liquid equilibrium studies (see the Examples), whosecomposition at atmospheric pressure is about 50% w/w R-1132a (49.8%),having an atmospheric boiling point of about −85.7° C. The azeotropiccomposition increases to about 53% w/w R-1132a at 30 bara. Thus, in apreferred embodiment, the invention provides an azeotropic ornear-azeotropic composition comprising R-1132a and R-116. A furtherpreferred composition of the invention comprises from about 45 to about60% by weight of R-1132a and from about 40 to about 55% by weight ofR-116.

By azeotropic composition, we include the meaning of a binarycomposition which at vapour-liquid equilibrium has the same compositionin both phases, and whose boiling point is lower than that of either ofthe pure components. By near-azeotropic composition (e.g. anear-azeotropic composition of R-1132a and R-116), we include themeaning of binary liquid compositions whose vapour pressure is abovethat of the pure component with the lower boiling point (e.g. R-1132acompared to R-116) when measured at equivalent temperature, but whoseequilibrium vapour composition may differ from the liquid composition.

Certain compositions of the invention comprise R-1132a, R-116 and CO₂.In an embodiment, such compositions comprise R-1132a, R-116 and up toabout 70% by weight CO₂.

Advantageous compositions of the invention comprise from about 2 toabout 98% by weight of R-1132a, from about 2 to about 98% by weight ofR-116 and from about 2 to about 60% by weight CO₂.

Preferred compositions of the invention comprise from about 4 to about96% by weight of R-1132a, from about 4 to about 96% by weight of R-116and from about 4 to about 50% by weight CO₂. Such compositions maycontain from about 6 to about 40% by weight CO₂, for example from about8 to about 30% by weight CO₂.

In a preferred embodiment, the amount of CO₂ in the compositions of theinvention is less than about 20% by weight, preferably less than about15% by weight, for example less than about 13% by weight. It is believedthat by limiting the CO₂ content to such levels, undesirable dry ice(solid CO₂) formation can be reduced or avoided during use of thecompositions of the invention as refrigerants.

Further advantageous compositions of the invention contain from about 5to about 60% by weight of R-1132a, from about 30 to about 70% by weightof R-116 and from about 2 to about 20% by weight CO₂. Such compositionstypically contain from about 10 to about 50% by weight of R-1132a, fromabout 40 to about 70% by weight of R-116 and from about 5 to about 15%by weight CO₂, or from about 40 to about 60% by weight of R-1132a, fromabout 35 to about 55% by weight of R-116 and from about 5 to about 20%by weight CO₂. In one embodiment, the compositions of the inventioncontain up to about 35% by weight of R-1132a, at least about 55% byweight of R-116 and up to about 13% by weight CO₂.

Certain compositions of the invention comprise R-1132a and ethane(R-170), typically from about 20 to about 99% by weight of R-1132a andfrom about 1 to about 80% by weight of R-170. A preferred suchcomposition comprises from about 50 to about 99% by weight of R-1132aand from about 1 to about 50% by weight of R-170.

A another preferred composition of the invention comprises from about 75to about 99% by weight of R-1132a and from about 1 to about 25% byweight of R-170.

A binary minimum-boiling azeotrope has been identified between R-1132aand R-170 by vapour-liquid equilibrium studies (see the Examples), whosecomposition varies with temperature, from about 54% by weight R-170 at0° C. to about 41% by weight R-170 at −80° C. In a preferred embodiment,the invention provides an azeotropic or near-azeotropic compositioncomprising R-1132a and R-170. A further preferred composition of theinvention comprises from about 40 to about 60% by weight of R-1132a andfrom about 40 to about 60% by weight of R-170.

Certain compositions of the invention comprise R-1132a, R-170 and CO₂.In an embodiment, such compositions comprise R-1132a, R-170 and up toabout 70% by weight CO₂.

Advantageous compositions of the invention comprise from about 2 toabout 98% by weight of R-1132a, from about 2 to about 98% by weight ofR-170 and from about 2 to about 60% by weight CO₂.

Preferred compositions of the invention comprise from about 4 to about96% by weight of R-1132a, from about 4 to about 96% by weight of R-170and from about 4 to about 50% by weight CO₂. Such compositions maycontain from about 6 to about 40% by weight CO₂, for example from about8 to about 30% by weight CO₂. In one aspect, as previously described,the amount of CO₂ in such compositions comprising R-1132a, R-170 and CO₂is less than about 20% by weight, preferably less than about 15% byweight, for example less than about 13% by weight.

Certain compositions of the invention comprise R-1132a, R-116 and R-170.

Advantageous compositions of the invention comprise from about 4 toabout 70% by weight of R-1132a, from about 4 to about 96% by weight ofR-116 and from about 4 to about 92% by weight R-170.

Preferred compositions of the invention comprise from about 4 to about70% by weight of R-1132a, from about 4 to about 88% by weight of R-116and from about 8 to about 92% by weight R-170.

Yet further compositions of the invention consist of quaternary mixturesof ethane, carbon dioxide, R-1132a and R-116. Preferred embodiments ofthese quaternary compositions are those in which the bulk compositioncan be assessed as non-flammable by the ASHRAE-34 methodology.Advantageously, the combined amount of ethane and carbon dioxide makesup less than 50% by weight of the composition. Preferably, suchcompositions contain at least as much CO₂ as ethane (by weight),preferably twice as much CO₂ as ethane (by weight).

Advantageous compositions comprise from about 2 to about 20% by weightethane, from about 2 to about 45% by weight CO₂, from about 15 to about85% by weight R-1132a and from about 5 to about 80% by weight R-116.Preferred compositions comprise from about 4 to about 12% by weightethane, from about 4 to about 40% by weight CO₂, from about 20 to about80% by weight R-1132a and from about 8 to about 76% by weight R-116.

Any of the above described compositions may additionally containpentafluoroethane (R-125).

Any of the above described compositions may further contain ahydrocarbon, wherein the hydrocarbon is in addition to any ethanepresent in the composition. Advantageously, the hydrocarbon is one ormore compound(s) selected from the group consisting of propane, propene,isobutane, n-butane, n-pentane, isopentane and mixtures thereof. In apreferred embodiment, the hydrocarbon comprises n-pentane.

Without being bound by theory, it is believed that, when present, theinclusion of ethane and/or an additional hydrocarbon compound mayenhance oil miscibility, solubility and/or return characteristics.Preferably, the compositions of the invention preferably contain fromabout 1 to about 50% by weight of the hydrocarbon component, for examplefrom about 1 to about 20%.

All of the chemicals herein described are commercially available. Forexample, the fluorochemicals may be obtained from Apollo Scientific (UK)and carbon dioxide may be obtained from liquefied gas suppliers such asLinde AG.

As used herein, all % amounts mentioned in compositions herein,including in the claims, are by weight based on the total weight of thecompositions, unless otherwise stated.

By the term “about”, as used in connection with numerical values ofamounts of components in % by weight, we include the meaning of ±0.5% byweight, for example ±0.2% by weight or ±0.1% by weight.

For the avoidance of doubt, it is to be understood that the stated upperand lower values for ranges of amounts of components in the compositionsof the invention described herein may be interchanged in any way,provided that the resulting ranges fall within the broadest scope of theinvention.

In an embodiment, the compositions of the invention are substantiallyfree of any component that has heat transfer properties (other than thecomponents specified).

For instance, the compositions of the invention may be substantiallyfree of any other hydrofluorocarbon compound (other than R-1132a, R-116and optionally R-125).

Any of the compositions of the invention described herein, includingthose with specifically defined amounts of R-1132a, the second componentand, optionally, CO₂, may consist essentially of (or consist of) theamounts of R-1132a, the second component and, optionally, CO₂ defined inthose compositions.

By the term “consist essentially of”, we include the meaning that thecompositions of the invention contain substantially no other components,particularly no further hydrofluorocarbon compounds known to be used inheat transfer compositions (e.g. hydrofluoroalkanes orhydrofluoroalkenes). We include the term “consist of” within the meaningof “consist essentially of”.

By “substantially no” and “substantially free of”, we include themeaning that the compositions of the invention contain 0.5% by weight orless of the stated component, preferably 0.1% or less, based on thetotal weight of the composition.

The compositions of the invention have zero ozone depletion potential

Typically, the compositions of the invention have a GWP of less thanabout 12000, such as less than about 11000.

In one embodiment, the compositions of the invention comprising R-1132aand R-116 have a GWP of less than about 11000, preferably less thanabout 10500 or about 10000 or about 9000 or about 8000.

In one aspect, the compositions of the invention comprising R-1132a,R-116 and CO₂ have a GWP of less than about 11000, for instance lessthan about 10000, e.g. from about 100 to about 10000, or from about 100to about 7000

Typically, the compositions of the invention comprising R-1132a andR-170 have a GWP of about 4 or less.

Typically, the compositions of the invention comprising R-1132a, R-170and CO₂ have a GWP of about 4 or less.

In one embodiment, the compositions of the invention comprising R-1132a,R-170, R-116 and CO₂ have a GWP of less than about 10000, for instanceless than about 9000, e.g. from about 1000 to about 8000, or from about2000 to about 7000.

Typically, the compositions of the subject invention are of reducedflammability hazards when compared to R-1132a.

Flammability may be determined in accordance with ASHRAE Standard 34incorporating the ASTM Standard E-681 with test methodology as perAddendum 34p dated 2004, the entire content of which is incorporatedherein by reference.

In one aspect, the compositions have one or more of (a) a higher lowerflammable limit; (b) a higher ignition energy (sometimes referred to asauto ignition energy or pyrolysis); or (c) a lower flame velocitycompared to R-1132a alone. Preferably, the compositions of the inventionare less flammable compared to R-1132a in one or more of the followingrespects: lower flammable limit at 23° C.; lower flammable limit at 60°C.; breadth of flammable range at 23° C. or 60° C.; auto-ignitiontemperature (thermal decomposition temperature); minimum ignition energyin dry air or flame speed. The flammable limits being determinedaccording to the methods specified in ASHRAE-34 and the auto-ignitiontemperature being determined in a 500 ml glass flask by the method ofASTM E659-78.

In a preferred embodiment, the compositions of the invention arenon-flammable. For example, the compositions of the invention arenon-flammable at a test temperature of 60° C. using the ASHRAE-34methodology. Advantageously, the mixtures of vapour that exist inequilibrium with the compositions of the invention at any temperaturebetween about −20° C. and 60° C. are also non-flammable.

Certain non-flammable compositions of the invention are described in theExamples. A preferred non-flammable composition of the inventioncomprises (optionally consists essentially of or consists of) up toabout 30% by weight R-1132a and at least about 70% by weight R116.

In some applications it may not be necessary for the formulation to beclassed as non-flammable by the ASHRAE-34 methodology; it is possible todevelop fluids whose flammability limits will be sufficiently reduced inair to render them safe for use in the application, for example if it isphysically not possible to make a flammable mixture by leaking therefrigeration equipment charge into the surrounds. Certain such reducedflammability compositions of the invention are described in theExamples.

In one embodiment, the compositions of the invention have a flammabilityclassifiable as 1 or 2 L according to the ASHRAE standard 34classification method

The compositions of the invention, particularly those comprisingR-1132a, R-116 and CO₂, advantageously have a temperature glide in anevaporator or a condenser of less than 10 K. Preferably suchcompositions have a temperature glide of less than about 5 K, and evenmore preferably less than about 1 K.

The critical temperature of a heat transfer composition should be higherthan the maximum expected condenser temperature. This is because thecycle efficiency drops as critical temperature is approached. As thishappens, the latent heat of the refrigerant is reduced and so more ofthe heat rejection in the condenser takes place by cooling gaseousrefrigerant; this requires more area per unit heat transferred. Thecritical temperature of R-508B is about 11° C. (data estimated byREFPROP).

In one aspect, the compositions of the invention have a criticaltemperature of greater than about 0° C., preferably greater than about11° C.

It is believed that the compositions of the invention exhibit acompletely unexpected combination of low-/non-flammability, low GWP,improved lubricant miscibility and improved refrigeration performanceproperties. Some of these refrigeration performance properties areexplained in more detail below.

The compositions of the invention typically have a volumetricrefrigeration capacity that is at least 85% of that of R-508.Preferably, the compositions of the invention have a volumetricrefrigeration capacity that is at least 90% of that of R-508, forexample from about 95% to about 120% of that of R-508

The compositions of the invention typically are capable of reachingtemperatures of −70° C. or lower, preferably −80° C. or lower, forexample −85° C. or lower whilst maintain the evaporation pressure aboveatmospheric pressure.

In one embodiment, the cycle efficiency (Coefficient of Performance,COP) of the compositions of the invention is within about 5% or evenbetter than the existing refrigerant fluid it is replacing.Conveniently, the compressor discharge temperature of the compositionsof the invention is within about 15K of the existing refrigerant fluidit is replacing, preferably about 10K or even about 5K.

The compositions of the invention are typically suitable for use inexisting designs of equipment, for example, ULT refrigeration equipmentand are compatible with all classes of lubricant currently used withestablished HFC refrigerants. They may be optionally stabilised orcompatibilised with mineral oils by the use of appropriate additives.

Preferably, when used in heat transfer equipment, the composition of theinvention is combined with a lubricant.

Conveniently, the lubricant is selected from the group consisting ofmineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters(POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAGesters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinationsthereof. PAGs and POEs are currently preferred lubricants for thecompositions of the invention.

Advantageously, the lubricant further comprises a stabiliser.

Preferably, the stabiliser is selected from the group consisting ofdiene-based compounds, phosphates, phenol compounds and epoxides, andmixtures thereof.

Conveniently, the composition of the invention may be combined with aflame retardant.

Advantageously, the flame retardant is selected from the groupconsisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminium trihydrate, polyvinyl chloride, a fluorinatediodocarbon, a fluorinated bromocarbon, trifluoro iodomethane,perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

In one embodiment, the invention provides a heat transfer devicecomprising a composition of the invention.

Preferably, the heat transfer device is a refrigeration device.

Conveniently, the heat transfer device is an ultra-low temperaturerefrigeration system.

Advantageously, the heat transfer device contains a cascade system.

The invention also provides the use of a composition of the invention ina heat transfer device as herein described.

According to another aspect of the invention, there is provided asprayable composition comprising a material to be sprayed and apropellant comprising a composition of the invention.

According to a further aspect of the invention, there is provided amethod for cooling an article which comprises condensing a compositionof the invention and thereafter evaporating said composition in thevicinity of the article to be cooled.

According to another aspect of the invention, there is provided a methodfor heating an article which comprises condensing a composition of theinvention in the vicinity of the article to be heated and thereafterevaporating said composition.

According to a further aspect of the invention, there is provided amethod for extracting a substance from biomass comprising contacting thebiomass with a solvent comprising a composition of the invention, andseparating the substance from the solvent.

According to another aspect of the invention, there is provided a methodof cleaning an article comprising contacting the article with a solventcomprising a composition of the invention.

According to a further aspect of the invention, there is provided amethod for extracting a material from an aqueous solution comprisingcontacting the aqueous solution with a solvent comprising a compositionof the invention, and separating the material from the solvent.

According to another aspect of the invention, there is provided a methodfor extracting a material from a particulate solid matrix comprisingcontacting the particulate solid matrix with a solvent comprising acomposition of the invention, and separating the material from thesolvent.

According to a further aspect of the invention, there is provided amechanical power generation device containing a composition of theinvention.

Preferably, the mechanical power generation device is adapted to use aRankine Cycle or modification thereof to generate work from heat.

According to another aspect of the invention, there is provided a methodof retrofitting a heat transfer device comprising the step of removingan existing heat transfer fluid, and introducing a composition of theinvention. Preferably, the heat transfer device is a refrigerationdevice, more preferably still the device is an ultra-low temperaturerefrigeration system. Advantageously, the method further comprises thestep of obtaining an allocation of greenhouse gas (e.g. carbon dioxide)emission credit.

In accordance with the retrofitting method described above, an existingheat transfer fluid can be fully removed from the heat transfer devicebefore introducing a composition of the invention. An existing heattransfer fluid can also be partially removed from a heat transferdevice, followed by introducing a composition of the invention.

The compositions of the invention may also be prepared simply by mixingthe R-1132a, the second component (and optional components such asR-744, R-125, hydrocarbons, a lubricant, a stabiliser or an additionalflame retardant) in the desired proportions. The compositions can thenbe added to a heat transfer device (or used in any other way as definedherein).

In a further aspect of the invention, there is provided a method forreducing the environmental impact arising from operation of a productcomprising an existing compound or composition, the method comprisingreplacing at least partially the existing compound or composition with acomposition of the invention. Preferably, this method comprises the stepof obtaining an allocation of greenhouse gas emission credit.

By environmental impact we include the generation and emission ofgreenhouse warming gases through operation of the product.

As mentioned above, this environmental impact can be considered asincluding not only those emissions of compounds or compositions having asignificant environmental impact from leakage or other losses, but alsoincluding the emission of carbon dioxide arising from the energyconsumed by the device over its working life. Such environmental impactmay be quantified by the measure known as Total Equivalent WarmingImpact (TEWI). This measure has been used in quantification of theenvironmental impact of certain stationary refrigeration and airconditioning equipment, including for example supermarket refrigerationsystems (see, for example,en.wikipedia.org/wiki/Total_equivalent_warming_impact).

The environmental impact may further be considered as including theemissions of greenhouse gases arising from the synthesis and manufactureof the compounds or compositions. In this case the manufacturingemissions are added to the energy consumption and direct loss effects toyield the measure known as Life-Cycle Carbon Production (LCCP, see forexample sae.org/events/aars/presentations/2007papasavva.pdf). The use ofLCCP is common in assessing environmental impact of automotive airconditioning systems.

Emission credit(s) are awarded for reducing pollutant emissions thatcontribute to global warming and may, for example, be banked, traded orsold. They are conventionally expressed in the equivalent amount ofcarbon dioxide. Thus if the emission of 1 kg of R-134a is avoided thenan emission credit of 1×1300=1300 kg CO₂ equivalent may be awarded.

In another embodiment of the invention, there is provided a method forgenerating greenhouse gas emission credit(s) comprising (i) replacing anexisting compound or composition with a composition of the invention,wherein the composition of the invention has a lower GWP than theexisting compound or composition; and (ii) obtaining greenhouse gasemission credit for said replacing step.

In a preferred embodiment, the use of the composition of the inventionresults in the equipment having a lower Total Equivalent Warming Impact,and/or a lower Life-Cycle Carbon Production than that which would beattained by use of the existing compound or composition.

These methods may be carried out on any suitable product, for example inthe fields of air-conditioning, refrigeration (e.g. low and mediumtemperature refrigeration), heat transfer, aerosols or sprayablepropellants, gaseous dielectrics, flame suppression, solvents (e.g.carriers for flavorings and fragrances), cleaners, topical anesthetics,and expansion applications. Preferably, the field is ultra-lowtemperature refrigeration.

Examples of suitable products include heat transfer devices, sprayablecompositions, solvents and mechanical power generation devices. In apreferred embodiment, the product is a heat transfer device, such as arefrigeration device or an ultra-low temperature refrigeration system.

The existing compound or composition has an environmental impact asmeasured by GWP and/or TEWI and/or LCCP that is higher than thecomposition of the invention which replaces it. The existing compound orcomposition may comprise a fluorocarbon compound, such as a perfluoro-,hydrofluoro-, chlorofluoro- or hydrochlorofluoro-carbon compound or itmay comprise a fluorinated olefin.

Preferably, the existing compound or composition is a heat transfercompound or composition such as a refrigerant. Examples of refrigerantsthat may be replaced include ULT refrigerants such as R-508A, R-508B,R23 and R13B1.

Any amount of the existing compound or composition may be replaced so asto reduce the environmental impact. This may depend on the environmentalimpact of the existing compound or composition being replaced and theenvironmental impact of the replacement composition of the invention.Preferably, the existing compound or composition in the product is fullyreplaced by the composition of the invention.

The invention is illustrated by the following non-limiting examples.

EXAMPLES

Binary Mixtures of R-1132a and R-116

A binary minimum-boiling azeotrope between R-1132a and R-116 wasidentified by study of the vapour-liquid equilibrium of binary mixturesover a temperature range of −70° C. to 0° C. using a constant-volumeapparatus. The data thus generated were regressed to a thermodynamicmodel capable of extrapolation from the measurement temperature/pressurerange to atmospheric pressure conditions.

The experimental data were measured in a static constant-volumeapparatus consisting of a vessel of precisely-known internal volumelocated in a temperature-controlled metal block. A magnetic stirringdevice was located inside the vessel. Refrigerated fluid was passedthrough the block to allow precise control of temperature inside thevessel. The cell was evacuated then known amounts of each component werethen charged to the cell. The temperature of the cell was then variedstepwise from about −70° C. to 0° C. At each temperature the celltemperature and pressure were logged continuously and recorded whenstable conditions were reached.

The resulting datasets were then regressed using Barker's method (asdescribed in The Properties of Gases and Liquids 3^(rd) edition (Reid,Sherwood & Prausnitz), which is incorporated herein by reference) to athermodynamic model capable of representing non-ideal vapour liquidequilibria. The model used the Redlich Kwong equation of state torepresent the gas phase properties and the Wilson equation to representthe non-ideality of the liquid phase mixture, as described in Reid etal.

The phase behaviour of this system is illustrated in FIGS. 1 and 2. FIG.1 shows the vapour composition in the mixture (inferred using theregressed model) plotted against the equilibrium liquid composition. Itis seen that the azeotropic point (where the vapour and liquidcompositions coincide) moves with pressure, increasing in R-1132acontent.

A feature of the R-1132a/R-116 binary system identified is that thevapour pressure of any binary mixture containing more than about 14% w/wR-1132a is equal to or higher than the vapour pressure of R-1132a itself(the more volatile component of the system). This is illustrated in FIG.2. This means that the refrigeration performance of binary mixtures ofthe fluids is unexpectedly enhanced compared to that which could beexpected from considering the fluid as an ideal binary mixture. Inparticular we have found that compositions of more than about 35% w/wR-1132a will exhibit higher refrigeration capacity and improvedvolumetric compressor efficiency than pure R-1132a in typical lowtemperature refrigeration cycle conditions.

FIG. 3 shows calculated refrigeration cycle performance for binarycompositions of the invention, with vapour liquid equilibrium modelledbased on the measured phase equilibrium, together with a comparison madeto the same compositions assuming Raoult's Law (ideal) behaviour. Thethermodynamic properties of R-116 used in this cycle modelling weretaken from the NIST REFPROP software version 8. Properties of R-1132awere taken from available open literature data with the exception ofsaturated liquid vapour pressure, which was measured by us in thedetermination of the phase equilibrium data. The main source of data forR-1132a physical properties was the commercial PPDS thermodynamic datapackage provided by TUV-NEL, augmented with data from the commercialDECHEMA database.

The cycle conditions for the modelling were as follows.

TABLE 1 Cycle conditions for R-1132a/R-116 binary system modelling Cycleconditions for modelling Condensing temperature ° C. −40 Evaporatingtemperature ° C. −85 Suction temperature ° C. −40 Isentropic efficiency  65% Subcooling K  5 Evaporator superheat K  5 Compressor clearanceratio    4%

The modelled data is set out in the following table. The GWP values forthe binary mixtures shown are calculated on the basis of GWP values of 4and 12200 for R-1132a and R-116, respectively. By way of reference, thecorresponding volumetric capacity for pure R-1132a using the samecalculations is 726.

TABLE 2 Refrigeration performance modelling data for R-1132a/R-116binary system R1132a (weight %)    4%    8%   12%   16%   20%   24% R116(weight %) 96.00% 92.00% 88.00% 84.00% 80.00% 76.00% GWP 11712 1122410736 10249 9761 9273 Evaporator pressure bar 0.75 0.80 0.85 0.89 0.930.96 Condenser pressure bar 5.82 6.16 6.44 6.68 6.87 7.04 Pressure ratio7.78 7.68 7.57 7.47 7.39 7.31 Volumetric efficiency  84.2%  84.6%  84.9% 85.3%  85.6%  85.8% Discharge temperature ° C. −12.1 −10.5 −9.3 −8.2−7.2 −6.4 Volumetric flowrate m³/hr 62.2 58.9 56.4 54.5 52.9 51.6Evaporator temp glide K 0.8 1.3 1.6 1.6 1.4 1.2 Condenser temp glide K1.2 1.7 1.8 1.6 1.3 1.0 Volumetric capacity kJ/m³ 579 611 638 661 681698 Cooling COP 2.29 2.26 2.24 2.21 2.20 2.19 R1132a (weight %)   28%  32%   36%   40%   44%   48% R116 (weight %) 72.00% 68.00% 64.00%60.00% 56.00% 52.00% GWP 8785 8297 7809 7322 6834 6346 Evaporatorpressure bar 0.99 1.01 1.03 1.04 1.05 1.05 Condenser pressure bar 7.177.27 7.34 7.39 7.41 7.42 Pressure ratio 7.24 7.18 7.14 7.10 7.07 7.05Volumetric efficiency  86.1%  86.3%  86.5%  86.7%  86.8%  86.9%Discharge temperature ° C. −5.5 −4.7 −3.9 −3.1 −2.2 −1.3 Volumetricflowrate m³/hr 50.5 49.6 48.9 48.3 47.9 47.6 Evaporator temp glide K 0.90.6 0.4 0.2 0.1 0.0 Condenser temp glide K 0.7 0.4 0.2 0.1 0.0 0.0Volumetric capacity kJ/m³ 713 726 737 746 752 757 Cooling COP 2.18 2.172.17 2.17 2.17 2.18 R1132a (weight %)   52%   56%   60%   64%   68%  72% R116 (weight %) 48.00% 44.00% 40.00% 36.00% 32.00% 28.00% GWP 58585370 4882 4395 3907 3419 Evaporator pressure bar 1.05 1.05 1.04 1.041.03 1.02 Condenser pressure bar 7.41 7.39 7.36 7.32 7.27 7.22 Pressureratio 7.05 7.05 7.06 7.07 7.08 7.10 Volumetric efficiency  87.0%  87.1% 87.2%  87.2%  87.3%  87.3% Discharge temperature ° C. −0.3 0.7 1.7 2.73.7 4.7 Volumetric flowrate m³/hr 47.4 47.3 47.3 47.4 47.5 47.6Evaporator temp glide K 0.0 0.1 0.1 0.2 0.3 0.3 Condenser temp glide K0.0 0.1 0.1 0.2 0.3 0.3 Volumetric capacity kJ/m³ 760 761 761 760 758756 Cooling COP 2.18 2.19 2.19 2.20 2.20 2.21 R1132a (weight %)   76%  80%   84%   88%   92%   96% R116 (weight %) 24.00% 20.00% 16.00%12.00%  8.00%  4.00% GWP 2931 2443 1955 1468 980 492 Evaporator pressurebar 1.01 0.99 0.98 0.97 0.96 0.94 Condenser pressure bar 7.16 7.10 7.046.97 6.90 6.83 Pressure ratio 7.12 7.14 7.16 7.19 7.21 7.24 Volumetricefficiency  87.4%  87.4%  87.4%  87.4%  87.4%  87.4% Dischargetemperature ° C. 5.7 6.6 7.5 8.4 9.2 10.0 Volumetric flowrate m³/hr 47.848.0 48.3 48.6 48.9 49.2 Evaporator temp glide K 0.4 0.4 0.4 0.3 0.2 0.1Condenser temp glide K 0.4 0.4 0.4 0.3 0.2 0.1 Volumetric capacity kJ/m³753 750 746 741 737 731 Cooling COP 2.22 2.22 2.23 2.24 2.24 2.25

The data show that for compositions between about 32% and 76% R-1132athe evaporation pressure is greater than atmospheric pressure and thecooling capacity is greater than that of R-1132a alone.

Binary Mixtures of R-170 and R-1132a

The phase equilibrium behaviour of mixtures of ethane and R-1132a wasstudied in the temperature range −80 to 0° C. using data generated usingPHYSPACK-PPB with WERK streamtype and binary interaction parametersoptimised to fit Mexichem VLE data. The results are shown in the tablebelow and the bubble point pressure of R-170/R-1132a mixtures at −40° C.is shown in FIG. 4.

TABLE 3 Binary VLE data for R-170/R-1132a mixtures Bubble Ideal StreamLiq Mass Vap Mass Point bubble Temperature Stream Fr Fr Pressurepressure ° C. Molar VF ETHANE ETHANE bar bar −80 0 0 0 1.21798 1.21798−80 0 0.05 0.0972247 1.35928 1.25446 −80 0 0.1 0.171521 1.45689 1.28723−80 0 0.15 0.231542 1.52581 1.31683 −80 0 0.2 0.282277 1.57523 1.34371−80 0 0.25 0.32683 1.61097 1.36822 −80 0 0.3 0.367258 1.6368 1.39066 −800 0.35 0.405006 1.65522 1.41128 −80 0 0.4 0.441142 1.6679 1.4303 −80 00.45 0.476504 1.67597 1.4479 −80 0 0.5 0.511787 1.68023 1.46422 −80 00.55 0.5476 1.68123 1.47941 −80 0 0.6 0.584512 1.67933 1.49358 −80 00.65 0.623085 1.67481 1.50682 −80 0 0.7 0.663903 1.66785 1.51923 −80 00.75 0.707603 1.65859 1.53087 −80 0 0.8 0.754905 1.6471 1.54183 −80 00.85 0.806652 1.63345 1.55216 −80 0 0.9 0.86386 1.61768 1.5619 −80 00.95 0.927781 1.5998 1.57112 −80 0 1 1 1.57985 1.57985 −40 0 0 0 6.754036.75403 −40 0 0.05 0.077327 7.26181 6.85829 −40 0 0.1 0.141724 7.624446.95196 −40 0 0.15 0.197337 7.88483 7.03659 −40 0 0.2 0.246867 8.071587.11342 −40 0 0.25 0.29217 8.20405 7.18348 −40 0 0.3 0.334581 8.295537.24763 −40 0 0.35 0.375101 8.35529 7.30658 −40 0 0.4 0.414517 8.38997.36095 −40 0 0.45 0.453476 8.40407 7.41125 −40 0 0.5 0.492531 8.401247.45792 −40 0 0.55 0.532183 8.38395 7.50133 −40 0 0.6 0.572899 8.354117.54182 −40 0 0.65 0.615145 8.31317 7.57967 −40 0 0.7 0.659393 8.262287.61514 −40 0 0.75 0.706148 8.20233 7.64844 −40 0 0.8 0.755966 8.134057.67976 −40 0 0.85 0.809469 8.05804 7.70927 −40 0 0.9 0.867381 7.974817.73713 −40 0 0.95 0.930551 7.88481 7.76348 −40 0 1 1 7.78842 7.78842 00 0 0 22.1119 22.1119 0 0 0.05 0.0634704 23.2491 22.299 0 0 0.1 0.1204724.0949 22.4671 0 0 0.15 0.17285 24.7165 22.619 0 0 0.2 0.221933 25.163322.7568 0 0 0.25 0.268696 25.4729 22.8825 0 0 0.3 0.31388 25.673922.9977 0 0 0.35 0.358073 25.7881 23.1035 0 0 0.4 0.401746 25.832723.201 0 0 0.45 0.445298 25.8214 23.2913 0 0 0.5 0.489069 25.7646 23.3750 0 0.55 0.533365 25.671 23.4529 0 0 0.6 0.578466 25.5474 23.5256 0 00.65 0.624636 25.3992 23.5935 0 0 0.7 0.672132 25.2311 23.6572 0 0 0.750.721212 25.0465 23.7169 0 0 0.8 0.772136 24.8487 23.7731 0 0 0.850.825178 24.64 23.8261 0 0 0.9 0.880625 24.4226 23.8761 0 0 0.950.938786 24.1981 23.9234 0 0 1 1 23.9681 23.9681

The cycle conditions for the following modelling of R-1132a/R-170 blendswere as shown above for the modelling on the R-1132a/R-116 blends. Themodelled data is set out in the following table. The table also includesthe corresponding modelled data for R508B alone, R-1132a alone and R-116alone.

TABLE 4 Refrigeration performance modelling data for R-1132a/R-170binary system R170 (weight %)    4%    8%   12%   16%   20%   24%   28%R1132a (weight %) 96.00% 92.00% 88.00% 84.00% 80.00% 76.00% 72.00% GWP 44 4 4 4 4 4 Evaporator pressure bar 0.99 1.05 1.10 1.14 1.18 1.21 1.23Condenser pressure bar 7.10 7.39 7.62 7.82 7.98 8.11 8.22 Pressure ratio7.15 7.04 6.95 6.86 6.79 6.72 6.66 Volumetric efficiency  87.8%  88.1% 88.3%  88.6%  88.8%  89.0%  89.2% Discharge temperature ° C. 12.6 14.215.6 16.9 18.1 19.3 20.4 Evaporator temp glide K 0.6 0.9 1.1 1.1 1.0 0.80.6 Condenser temp glide K 0.6 0.9 0.9 0.8 0.7 0.5 0.3 Volumetriccapacity kJ/m³ 778 822 861 895 923 948 968 Cooling COP 2.28 2.30 2.312.32 2.33 2.34 2.34 R170 (weight %)   32%   36%   40%   44%   48%   52%  56% R1132a (weight %) 68.00% 64.00% 60.00% 56.00% 52.00% 48.00% 44.00%GWP 4 4 4 4 4 3 3 Evaporator pressure bar 1.25 1.27 1.29 1.29 1.30 1.301.30 Condenser pressure bar 8.30 8.35 8.38 8.40 8.40 8.39 8.37 Pressureratio 6.61 6.57 6.52 6.49 6.46 6.44 6.42 Volumetric efficiency  89.4% 89.6%  89.7%  89.8%  90.0%  90.1%  90.2% Discharge temperature ° C.21.5 22.6 23.7 24.8 25.9 27.0 28.1 Evaporator temp glide K 0.5 0.3 0.20.1 0.0 0.0 0.0 Condenser temp glide K 0.2 0.1 0.0 0.0 0.0 0.0 0.1Volumetric capacity kJ/m³ 985 999 1009 1017 1022 1025 1025 Cooling COP2.35 2.35 2.36 2.36 2.36 2.36 2.36 R170 (weight %)   60%   64%   68%  72%   76%   80%   84% R1132a (weight %) 40.00% 36.00% 32.00% 28.00%24.00% 20.00% 16.00% GWP 3 3 3 3 3 3 3 Evaporator pressure bar 1.30 1.301.30 1.29 1.28 1.28 1.27 Condenser pressure bar 8.34 8.30 8.26 8.21 8.168.10 8.04 Pressure ratio 6.40 6.39 6.38 6.37 6.36 6.35 6.35 Volumetricefficiency  90.3%  90.4%  90.4%  90.5%  90.6%  90.7%  90.7% Dischargetemperature ° C. 29.2 30.3 31.4 32.5 33.6 34.6 35.6 Evaporator tempglide K 0.0 0.0 0.1 0.1 0.1 0.1 0.0 Condenser temp glide K 0.1 0.1 0.20.2 0.2 0.2 0.2 Volumetric capacity kJ/m³ 1024 1022 1018 1014 1008 1002995 Cooling COP 2.36 2.35 2.35 2.35 2.34 2.34 2.34 R170 (weight %)   88%  92%   96% R1132a (weight %) 12.00%  8.00%  4.00% R508B R1132a R116 GWP3 3 3 13212 4 12200 Evaporator pressure bar 1.26 1.25 1.24 1.23 0.930.69 Condenser pressure bar 7.98 7.92 7.85 8.73 6.75 5.40 Pressure ratio6.34 6.34 6.34 7.12 7.26 7.85 Volumetric efficiency  90.8%  90.8%  90.9% 87.7%  87.5%  84.0% Discharge temperature ° C. 36.6 37.6 38.5 11.8 10.8−14.0 Evaporator temp glide K 0.1 0.1 0.0 0.1 0.0 0.0 Condenser tempglide K 0.2 0.2 0.1 0.1 0.0 0.0 Volumetric capacity kJ/m³ 988 981 973955 726 542 Cooling COP 2.33 2.33 2.32 2.30 2.26 2.32

Ternary Mixtures of R-744, R-1132a and R-116

Ternary compositions of carbon dioxide (R-744) with R-1132a and R-116have been identified which exhibit further enhanced refrigerationcapacity and reduced flammability compared to R-1132a. These have theadvantageous features that solid carbon dioxide formation in the lowpressure parts of the refrigeration system can be avoided and that lowercompressor discharge temperatures than those attainable with binaryR-744/R-1132a mixtures).

It is known in the thermodynamic literature (Valtz et al. Fluid PhaseEquilibria 258 (2007) 179-185, which is incorporated herein byreference) that the binary system of R-744/R-116 exhibits azeotropy attemperatures at least above −20° C. It has been found, surprisingly,that addition of R-744 to R-1132a and R-116 system significantlyenhances the refrigeration capacity of the resulting mixture by morethan would be expected if the mixture were an ideal mixture. Inparticular, regions of composition have been identified where theternary mixtures exhibits no or very low temperature glide in thetwo-phase region and only very small differences in phase composition.

The performance of selected ternary R-1132a/R-116/CO₂ compositions wasmodelled using the same cycle conditions and thermodynamic model asexplained in the previous examples. The VLE behaviour of the threebinary mixtures (R-744/R-116, R-744/R-1132a, R-1132a/R-116) wasregressed into the selected thermodynamic model and this was then usedto estimate performance. The data of Valtz were incorporated into thisregression.

The modelled data is set out in the following tables. The correspondingmodelled data for R508B alone, R-1132a alone and R-116 alone is shownabove in Table 4. The volumetric cooling capacity of selectedR-1132a/R-116/CO₂ blends is illustrated in FIG. 5.

Selected R-1132a/R-116/CO₂ blends of the invention offer an unexpectedcombination of benefits compared to R-508. These are: reduced compressordischarge temperature; reduced GWP and equivalent or enhancedrefrigeration capacity at constant compressor displacement.

Ternary Mixtures of R-744, R-1132a and R-170

The performance of selected ternary R-1132a/R-170/CO₂ compositions wasmodelled in accordance with the cycle conditions and thermodynamic modelas explained in the previous examples.

The modelled data is set out in the following tables.

Ternary Mixtures of R-116, R-1132a and R-170

The performance of selected ternary R-1132a/R-170/R-116 compositions wasmodelled in accordance with the cycle conditions and thermodynamic modelas explained in the previous examples.

The modelled data is set out in the following tables.

Quaternary Mixtures of R-116, R-744, R-1132a and R-170

The performance of selected ternary R-1132a/R-170/R-116/R-744compositions was modelled in accordance with the cycle conditions andthermodynamic model as explained in the previous examples.

The modelled data is set out in the following tables. The compositiontypically have capacity close to that of R508 whilst simultaneouslyavoiding having too flammable a vapour phase (e.g. less flammable thancorresponding ethane/R-1132a/R-116 blends) or too high a CO₂ contentcompared to corresponding CO₂/R-1132a/R-116 blends (which comparativelyhigh CO₂ content can lead to high compressor temperatures and potentialdry ice issues).

TABLE 5 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 4% by weight CO₂ R744 (weight %)    4%    4%    4%   4%    4%    4%    4%    4%    4%    4%    4%    4% R1132a (weight %) 4.0%  8.0%  12.0%  16.0%  20.0%  24.0%  28.0%  32.0%  36.0%  40.0% 44.0%  48.0% R116 (weight %) 92.00% 88.00% 84.00% 80.00% 76.00% 72.00%68.00% 64.00% 60.00% 56.00% 52.00% 48.00% GWP 11224 10736 10249 97619273 8785 8297 7809 7321 6834 6346 5858 Evaporator pressure bar 0.900.94 0.98 1.01 1.04 1.06 1.08 1.09 1.10 1.11 1.11 1.10 Condenserpressure bar 6.98 7.20 7.39 7.54 7.67 7.77 7.84 7.89 7.91 7.91 7.90 7.87Pressure ratio 7.74 7.63 7.54 7.45 7.38 7.32 7.26 7.21 7.17 7.15 7.137.12 Volumetric efficiency  84.6%  85.0%  85.3%  85.6%  85.9%  86.1% 86.3%  86.5%  86.7%  86.8%  87.0%  87.1% Discharge temperature ° C.−5.9 −5.0 −4.1 −3.4 −2.6 −2.0 −1.3 −0.6 0.2 1.0 1.8 2.8 Evaporator tempglide K 3.6 3.4 3.0 2.6 2.2 1.7 1.3 1.0 0.7 0.5 0.4 0.4 Condenser tempglide K 5.7 5.0 4.3 3.6 3.0 2.4 1.9 1.5 1.3 1.1 1.0 0.9 Volumetriccapacity kJ/m3 703 722 738 752 764 775 784 792 798 802 804 805 CoolingCOP 2.29 2.26 2.23 2.21 2.20 2.18 2.18 2.17 2.17 2.17 2.18 2.18 R744(weight %)    4%    4%    4%    4%    4%    4%    4%    4%    4%    4%   4%    4% R1132a (weight %)  52.0%  56.0%  60.0%  64.0%  68.0%  70.0% 76.0%  80.0%  84.0%  88.0%  92.0%   96% R116 (weight %) 44.00% 40.00%36.00% 32.00% 28.00% 26.00% 20.00% 16.00% 12.00%  8.00%  4.00%  0.00%GWP 5370 4882 4394 3907 3419 3175 2443 1955 1467 980 492 4 Evaporatorpressure bar 1.10 1.09 1.08 1.07 1.06 1.05 1.03 1.02 1.00 0.99 0.97 0.96Condenser pressure bar 7.82 7.77 7.71 7.65 7.58 7.54 7.43 7.35 7.27 7.197.11 7.02 Pressure ratio 7.12 7.13 7.14 7.16 7.17 7.18 7.21 7.23 7.257.28 7.30 7.33 Volumetric efficiency  87.1%  87.2%  87.3%  87.3%  87.3% 87.4%  87.4%  87.4%  87.4%  87.5%  87.5%  87.5% Discharge temperature °C. 3.7 4.7 5.7 6.6 7.6 8.0 9.4 10.2 11.1 11.9 12.7 13.4 Evaporator tempglide K 0.4 0.4 0.5 0.5 0.6 0.6 0.6 0.6 0.5 0.4 0.3 0.2 Condenser tempglide K 0.9 0.9 0.9 1.0 1.0 1.0 1.0 1.0 0.9 0.8 0.7 0.6 Volumetriccapacity kJ/m3 804 802 799 795 791 789 782 777 772 766 760 753 CoolingCOP 2.18 2.19 2.19 2.20 2.21 2.21 2.22 2.23 2.23 2.24 2.25 2.25

TABLE 6 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 8% by weight CO₂ R744 (weight %)  8.0%  8.0%  8.0% 8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% R1132a (weight %) 4.0%  8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% 44.0% 48.0%R116 (weight %) 88.0% 84.0% 80.0% 76.0% 72.0% 68.0% 64.0% 60.0% 56.0%52.0% 48.0% 44.0% GWP 10736 10248 9761 9273 8785 8297 7809 7321 68346346 5858 5370 Evaporator pressure bar 1.04 1.07 1.09 1.11 1.13 1.151.16 1.16 1.16 1.16 1.15 1.15 Condenser pressure bar 7.85 8.01 8.14 8.248.31 8.37 8.39 8.39 8.38 8.34 8.29 8.23 Pressure ratio 7.55 7.50 7.457.40 7.35 7.30 7.26 7.22 7.20 7.18 7.18 7.18 Volumetric efficiency 85.4%85.6% 85.8% 86.0% 86.2% 86.4% 86.6% 86.8% 86.9% 87.0% 87.1% 87.2%Discharge temperature ° C. −1.3 −0.6 0.1 0.7 1.3 2.0 2.6 3.3 4.0 4.9 5.76.7 Evaporator temp glide K 5.0 4.3 3.6 2.9 2.3 1.8 1.3 1.0 0.8 0.6 0.60.6 Condenser temp glide K 7.0 6.0 5.0 4.2 3.4 2.8 2.3 2.0 1.7 1.5 1.51.4 Volumetric capacity kJ/m3 805 812 819 827 833 840 845 848 850 849848 845 Cooling COP 2.29 2.25 2.23 2.20 2.19 2.18 2.17 2.17 2.17 2.172.18 2.18 R744 (weight %)  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% 8.0%  8.0%  8.0%  8.0% R1132a (weight %) 52.0% 56.0% 60.0% 64.0% 68.0%70.0% 76.0% 80.0% 84.0% 88.0% 92.0% R116 (weight %) 40.0% 36.0% 32.0%28.0% 24.0% 22.0% 16.0% 12.0%  8.0%  4.0%  0.0% GWP 4882 4394 3906 34192931 2687 1955 1467 979 492 4 Evaporator pressure bar 1.13 1.12 1.111.09 1.08 1.07 1.05 1.03 1.02 1.00 0.99 Condenser pressure bar 8.16 8.088.00 7.92 7.83 7.79 7.65 7.56 7.47 7.37 7.28 Pressure ratio 7.19 7.207.21 7.23 7.25 7.26 7.29 7.31 7.33 7.36 7.38 Volumetric efficiency 87.3%87.3% 87.3% 87.4% 87.4% 87.4% 87.5% 87.5% 87.5% 87.5% 87.5% Dischargetemperature ° C. 7.6 8.6 9.5 10.4 11.3 11.7 13.0 13.8 14.5 15.3 16.0Evaporator temp glide K 0.6 0.7 0.7 0.8 0.8 0.8 0.7 0.7 0.6 0.5 0.4Condenser temp glide K 1.4 1.4 1.4 1.5 1.5 1.5 1.4 1.3 1.3 1.1 1.0Volumetric capacity kJ/m3 841 836 831 826 820 817 808 801 794 787 779Cooling COP 2.18 2.19 2.20 2.20 2.21 2.21 2.22 2.23 2.24 2.24 2.25

TABLE 7 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 12% by weight CO₂ R744 (weight %) 12.0% 12.0% 12.0%12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% R1132a (weight %)  4.0% 8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% 44.0% R116 (weight%) 84.0% 80.0% 76.0% 72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0% 44.0% GWP10248 9760 9273 8785 8297 7809 7321 6833 6346 5858 5370 Evaporatorpressure bar 1.15 1.17 1.18 1.20 1.21 1.22 1.22 1.22 1.21 1.20 1.19Condenser pressure bar 8.55 8.66 8.75 8.81 8.85 8.86 8.84 8.81 8.75 8.698.61 Pressure ratio 7.45 7.43 7.39 7.35 7.32 7.28 7.25 7.23 7.22 7.227.23 Volumetric efficiency 85.9% 86.1% 86.3% 86.4% 86.6% 86.8% 86.9%87.0% 87.1% 87.2% 87.3% Discharge temperature ° C. 2.7 3.3 3.9 4.5 5.05.6 6.3 7.0 7.8 8.7 9.6 Evaporator temp glide K 5.0 4.1 3.4 2.7 2.1 1.61.2 0.9 0.8 0.7 0.7 Condenser temp glide K 6.8 5.7 4.8 3.9 3.3 2.7 2.32.0 1.8 1.7 1.7 Volumetric capacity kJ/m3 879 881 885 888 892 894 895895 893 889 884 Cooling COP 2.27 2.23 2.21 2.19 2.18 2.17 2.17 2.17 2.172.17 2.18 R744 (weight %) 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0%12.0% 12.0% 12.0% 12.0% R1132a (weight %) 48.0% 52.0% 56.0% 60.0% 64.0%68.0% 70.0% 76.0% 80.0% 84.0% 88.0% R116 (weight %) 40.0% 36.0% 32.0%28.0% 24.0% 20.0% 18.0% 12.0%  8.0%  4.0%  0.0% GWP 4882 4394 3906 34192931 2443 2199 1467 979 491 4 Evaporator pressure bar 1.18 1.16 1.151.13 1.12 1.10 1.09 1.06 1.05 1.03 1.01 Condenser pressure bar 8.52 8.438.34 8.24 8.14 8.04 7.98 7.83 7.73 7.63 7.52 Pressure ratio 7.24 7.257.26 7.28 7.30 7.32 7.33 7.36 7.38 7.40 7.43 Volumetric efficiency 87.3%87.4% 87.4% 87.5% 87.5% 87.5% 87.5% 87.5% 87.6% 87.6% 87.6% Dischargetemperature ° C. 10.5 11.4 12.3 13.2 14.0 14.9 15.3 16.4 17.2 17.9 18.6Evaporator temp glide K 0.7 0.8 0.8 0.9 0.9 0.9 0.9 0.8 0.7 0.6 0.5Condenser temp glide K 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.6 1.5 1.4 1.3Volumetric capacity kJ/m3 878 872 866 859 852 844 841 829 821 813 805Cooling COP 2.18 2.19 2.19 2.20 2.20 2.21 2.22 2.23 2.23 2.24 2.25

TABLE 8 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 16% by weight CO₂ R744 (weight %) 16.0% 16.0% 16.0%16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% R1132a (weight %)  4.0% 8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% 44.0% R116 (weight%) 80.0% 76.0% 72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0% 44.0% 40.0% GWP9760 9272 8785 8297 7809 7321 6833 6345 5858 5370 4882 Evaporatorpressure bar 1.23 1.25 1.26 1.27 1.27 1.27 1.27 1.26 1.25 1.23 1.22Condenser pressure bar 9.13 9.21 9.26 9.29 9.29 9.26 9.21 9.14 9.06 8.978.87 Pressure ratio 7.40 7.38 7.36 7.33 7.30 7.27 7.26 7.25 7.26 7.267.28 Volumetric efficiency 86.4% 86.5% 86.7% 86.8% 86.9% 87.1% 87.2%87.3% 87.3% 87.4% 87.4% Discharge temperature ° C. 6.4 7.0 7.5 8.0 8.69.2 9.9 10.7 11.6 12.4 13.3 Evaporator temp glide K 4.4 3.5 2.8 2.1 1.61.2 1.0 0.8 0.8 0.8 0.8 Condenser temp glide K 6.0 5.0 4.1 3.4 2.8 2.42.1 1.9 1.8 1.8 1.8 Volumetric capacity kJ/m3 937 937 939 940 941 940938 934 928 921 914 Cooling COP 2.24 2.21 2.19 2.18 2.17 2.17 2.17 2.172.17 2.17 2.18 R744 (weight %) 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0%16.0% 16.0% 16.0% R1132a (weight %) 48.0% 52.0% 56.0% 60.0% 64.0% 68.0%70.0% 76.0% 80.0% 84.0% R116 (weight %) 36.0% 32.0% 28.0% 24.0% 20.0%16.0% 14.0%  8.0%  4.0%  0.0% GWP 4394 3906 3418 2931 2443 1955 1711 979491 4 Evaporator pressure bar 1.20 1.18 1.17 1.15 1.13 1.11 1.10 1.081.06 1.04 Condenser pressure bar 8.76 8.65 8.54 8.43 8.32 8.20 8.15 7.987.87 7.76 Pressure ratio 7.29 7.30 7.32 7.34 7.36 7.38 7.39 7.42 7.447.47 Volumetric efficiency 87.5% 87.5% 87.5% 87.6% 87.6% 87.6% 87.6%87.6% 87.6% 87.6% Discharge temperature ° C. 14.2 15.1 16.0 16.8 17.618.4 18.8 19.8 20.5 21.2 Evaporator temp glide K 0.8 0.9 0.9 1.0 1.0 0.90.9 0.8 0.7 0.5 Condenser temp glide K 1.8 1.8 1.9 1.9 1.9 1.8 1.8 1.71.6 1.5 Volumetric capacity kJ/m3 906 898 890 882 874 865 861 848 839830 Cooling COP 2.18 2.19 2.19 2.20 2.21 2.21 2.22 2.23 2.24 2.24

TABLE 9 Refrigeration performance modelling data for R-1132a/R-116/CO2ternary system with 20% by weight CO2 R744 (weight %) 20.0% 20.0% 20.0%20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% R1132a (weight %)  4.0%  8.0%12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% R116 (weight %) 76.0%72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0% 44.0% 40.0% GWP 9272 8785 82977809 7321 6833 6345 5857 5370 4882 Evaporator pressure bar 1.31 1.321.32 1.33 1.32 1.32 1.31 1.29 1.27 1.26 Condenser pressure bar 9.63 9.689.70 9.69 9.65 9.59 9.51 9.41 9.30 9.19 Pressure ratio 7.38 7.36 7.337.31 7.29 7.28 7.28 7.29 7.30 7.31 Volumetric efficiency 86.8% 86.9%87.0% 87.1% 87.2% 87.3% 87.4% 87.5% 87.5% 87.6% Discharge temperature °C. 9.9 10.5 11.0 11.5 12.1 12.8 13.6 14.5 15.4 16.2 Evaporator tempglide K 3.4 2.7 2.0 1.5 1.1 0.9 0.8 0.7 0.7 0.8 Condenser temp glide K4.9 4.0 3.3 2.7 2.3 2.0 1.9 1.8 1.7 1.8 Volumetric capacity kJ/m3 985986 986 985 983 978 972 965 957 948 Cooling COP 2.21 2.19 2.18 2.17 2.172.17 2.17 2.17 2.17 2.17 R744 (weight %) 20.0% 20.0% 20.0% 20.0% 20.0%20.0% 20.0% 20.0% 20.0% 20.0% R1132a (weight %) 44.0% 48.0% 52.0% 56.0%60.0% 64.0% 68.0% 70.0% 76.0% 80.0% R116 (weight %) 36.0% 32.0% 28.0%24.0% 20.0% 16.0% 12.0% 10.0%  4.0%  0.0% GWP 4394 3906 3418 2930 24431955 1467 1223 491 3 Evaporator pressure bar 1.24 1.22 1.20 1.18 1.161.14 1.12 1.11 1.08 1.06 Condenser pressure bar 9.07 8.95 8.83 8.70 8.588.46 8.34 8.28 8.10 7.98 Pressure ratio 7.33 7.34 7.36 7.38 7.40 7.427.44 7.45 7.48 7.50 Volumetric efficiency 87.6% 87.6% 87.6% 87.7% 87.7%87.7% 87.7% 87.7% 87.7% 87.7% Discharge temperature ° C. 17.1 18.0 18.819.6 20.4 21.1 21.8 22.2 23.2 23.8 Evaporator temp glide K 0.8 0.9 0.91.0 1.0 1.0 0.9 0.9 0.7 0.6 Condenser temp glide K 1.8 1.8 1.9 1.9 1.91.9 1.9 1.8 1.7 1.6 Volumetric capacity kJ/m3 939 930 920 911 902 892883 878 863 853 Cooling COP 2.18 2.18 2.19 2.20 2.20 2.21 2.22 2.22 2.232.24

TABLE 10 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 24% by weight CO₂ R744 (weight %) 24.0%  24.0% 24.0%24.0% 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% R1132a (weight %)  4.0% 8.0%12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% R116 (weight %) 72.0%68.0% 64.0% 60.0% 56.0% 52.0% 48.0% 44.0% 40.0% 36.0% GWP 8784 8297 78097321 6833 6345 5857 5370 4882 4394 Evaporator pressure bar 1.37 1.371.37 1.37 1.36 1.35 1.33 1.31 1.29 1.27 Condenser pressure bar 10.0610.08 10.06 10.01 9.94 9.85 9.74 9.62 9.50 9.37 Pressure ratio 7.35 7.347.32 7.31 7.31 7.31 7.32 7.33 7.35 7.36 Volumetric efficiency 87.1%87.2% 87.3% 87.4% 87.5% 87.6% 87.6% 87.6% 87.7% 87.7% Dischargetemperature ° C. 13.4 13.9 14.4 15.1 15.8 16.6 17.4 18.3 19.2 20.0Evaporator temp glide K 2.4 1.8 1.3 1.0 0.8 0.7 0.6 0.7 0.7 0.8Condenser temp glide K 3.8 3.0 2.5 2.1 1.8 1.7 1.6 1.6 1.6 1.7Volumetric capacity kJ/m3 1029 1029 1026 1023 1017 1009 1000 990 980 970Cooling COP 2.19 2.18 2.17 2.17 2.16 2.16 2.16 2.17 2.17 2.18 R744(weight %) 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% R1132a(weight %) 44.0% 48.0% 52.0% 56.0% 60.0% 64.0% 68.0% 70.0% 76.0% R116(weight %) 32.0% 28.0% 24.0% 20.0% 16.0% 12.0%  8.0%  6.0%  0.0% GWP3906 3418 2930 2442 1955 1467 979 735 3 Evaporator pressure bar 1.251.23 1.21 1.19 1.17 1.15 1.13 1.12 1.09 Condenser pressure bar 9.23 9.108.97 8.83 8.70 8.57 8.44 8.38 8.19 Pressure ratio 7.38 7.40 7.41 7.437.45 7.47 7.49 7.50 7.54 Volumetric efficiency 87.7% 87.8% 87.8% 87.8%87.8% 87.8% 87.8% 87.8% 87.8% Discharge temperature ° C. 20.8 21.6 22.423.2 23.9 24.5 25.2 25.5 26.4 Evaporator temp glide K 0.9 0.9 1.0 1.01.0 0.9 0.8 0.8 0.6 Condenser temp glide K 1.8 1.8 1.9 1.9 1.9 1.9 1.81.8 1.6 Volumetric capacity kJ/m3 960 949 939 929 918 908 897 892 876Cooling COP 2.18 2.19 2.19 2.20 2.21 2.22 2.22 2.23 2.24

TABLE 11 Refrigeration performance modelling data for R-1132a/R-116/CO₂ternary system with 30% by weight CO₂ R744 (weight %) 30.0% 30.0% 30.0%30.0% 30.0% 30.0% 30.0% 30.0% 30.0% R1132a (weight %)  4.0%  8.0% 12.0%16.0% 20.0% 24.0% 28.0% 32.0% 36.0% R116 (weight %) 66.0% 62.0% 58.0%54.0% 50.0% 46.0% 42.0% 38.0% 34.0% GWP 8052 7565 7077 6589 6101 56135125 4638 4150 Evaporator pressure bar 1.44 1.44 1.43 1.41 1.39 1.371.35 1.33 1.31 Condenser pressure bar 10.58 10.54 10.47 10.38 10.2610.13 9.99 9.85 9.70 Pressure ratio 7.33 7.33 7.34 7.35 7.36 7.38 7.397.41 7.43 Volumetric efficiency 87.6% 87.7% 87.7% 87.8% 87.8% 87.8%87.9% 87.9% 87.9% Discharge temperature ° C. 18.5 19.2 19.9 20.8 21.622.5 23.3 24.1 24.9 Evaporator temp glide K 0.9 0.7 0.5 0.4 0.4 0.5 0.60.7 0.7 Condenser temp glide K 2.2 1.7 1.4 1.3 1.2 1.2 1.3 1.4 1.5Volumetric capacity kJ/m3 1087 1082 1074 1065 1054 1042 1031 1019 1007Cooling COP 2.17 2.16 2.16 2.16 2.16 2.16 2.16 2.17 2.17 R744 (weight %)30.0% 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% R1132a (weight %)40.0% 44.0% 48.0% 52.0% 56.0% 60.0% 64.0% 68.0% 70.0% R116 (weight %)30.0% 26.0% 22.0% 18.0% 14.0% 10.0%  6.0%  2.0%  0.0% GWP 3662 3174 26862198 1711 1223 735 247 3 Evaporator pressure bar 1.28 1.26 1.24 1.221.19 1.17 1.15 1.13 1.12 Condenser pressure bar 9.55 9.40 9.26 9.11 8.978.83 8.69 8.55 8.48 Pressure ratio 7.44 7.46 7.48 7.50 7.51 7.53 7.567.58 7.59 Volumetric efficiency 87.9% 87.9% 87.9% 88.0% 88.0% 88.0%88.0% 88.0% 88.0% Discharge temperature ° C. 25.7 26.4 27.1 27.8 28.429.0 29.6 30.2 30.5 Evaporator temp glide K 0.8 0.9 0.9 0.9 0.9 0.8 0.70.6 0.6 Condenser temp glide K 1.6 1.7 1.7 1.8 1.8 1.7 1.7 1.6 1.5Volumetric capacity kJ/m3 995 984 972 961 949 938 926 915 909 CoolingCOP 2.18 2.18 2.19 2.20 2.21 2.21 2.22 2.23 2.23

TABLE 12 Refrigeration performance modelling data for R-1132a/R-170/CO₂ternary system with 4% by weight CO₂ R744 (weight %)    4%    4%    4%   4%    4%    4%    4%    4%    4%    4%    4%    4% R170 (weight %) 4.0%  8.0%  12.0%  16.0%  20.0% 24.0%  28.0%  32.0%  36.0%  40.0% 44.0%  48.0% R1132a (weight %) 92.00% 88.00% 84.00% 80.00% 76.00%72.00% 68.00% 64.00% 60.00% 56.00% 52.00% 48.00% GWP 4 4 4 4 4 4 4 4 4 33 3 Evaporator pressure bar 1.02 1.08 1.13 1.18 1.22 1.25 1.28 1.30 1.321.33 1.34 1.35 Condenser pressure bar 7.38 7.68 7.92 8.13 8.30 8.43 8.548.62 8.67 8.71 8.72 8.72 Pressure ratio 7.21 7.09 6.99 6.90 6.83 6.756.69 6.63 6.58 6.54 6.50 6.47 Volumetric efficiency 87.8% 88.1% 88.4%88.6% 88.9% 89.1% 89.3% 89.4% 89.6% 89.8% 89.9% 90.0% Dischargetemperature ° C. 15.1 16.7 18.0 19.3 20.5 21.6 22.7 23.7 24.8 25.8 26.928.0 Evaporator temp glide K 0.8 1.2 1.3 1.3 1.2 1.1 0.9 0.8 0.6 0.5 0.50.4 Condenser temp glide K 1.2 1.4 1.5 1.4 1.2 1.1 0.9 0.8 0.8 0.7 0.80.8 Volumetric capacity kJ/m3 806 852 892 926 955 980 1002 1019 10331044 1052 1057 Cooling COP 2.27 2.29 2.30 2.31 2.32 2.33 2.33 2.34 2.342.34 2.34 2.35 R744 (weight %)    4%    4%    4%    4%    4%    4%    4%   4%    4%    4%    4%    4% R170 (weight %)  52.0%  56.0%  60.0% 64.0%  68.0%  70.0%  76.0%  80.0%  84.0%  88.0%  92.0%   96% R1132a(weight %) 44.00% 40.00% 36.00% 32.00% 28.00% 26.00% 20.00% 16.00%12.00%  8.00%  4.00%  0.00% GWP 3 3 3 3 3 3 3 3 3 3 3 3 Evaporatorpressure bar 1.35 1.35 1.35 1.35 1.34 1.34 1.33 1.32 1.32 1.31 1.30 1.29Condenser pressure bar 8.71 8.69 8.66 8.62 8.57 8.52 8.47 8.41 8.35 8.298.22 8.16 Pressure ratio 6.45 6.42 6.41 6.39 6.38 6.37 6.36 6.35 6.356.34 6.34 6.33 Volumetric efficiency  90.2%  90.3%  90.3%  90.4%  90.5% 90.6%  90.7%  90.7%  90.8%  90.8%  90.9%  91.0% Discharge temperature °C. 29.1 30.2 31.3 32.4 33.5 34.6 35.7 36.7 37.7 38.7 39.7 40.6Evaporator temp glide K 0.4 0.5 0.5 0.6 0.6 0.7 0.8 0.8 0.8 0.9 0.9 0.9Condenser temp glide K 0.9 0.9 1.0 1.1 1.2 1.3 1.3 1.4 1.4 1.5 1.5 1.4Volumetric capacity kJ/m3 1060 1061 1060 1057 1053 1049 1043 1037 10311024 1016 1008 Cooling COP 2.35 2.35 2.34 2.34 2.34 2.34 2.33 2.33 2.332.32 2.32 2.31

TABLE 13 Refrigeration performance modelling data for R-1132a/R-170/CO₂ternary system with 8% by weight CO₂ R744 (weight %)  8.0%  8.0%   8.0% 8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% R170 (weight %) 4.0%  8.0%  12.0%  16.0%  20.0%  24.0%  28.0%  32.0%  36.0%  40.0% 44.0% 48.0% R1132a (weight %)  88.0%  84.0%  80.0%  76.0%  72.0%  68.0% 64.0%  60.0%  56.0%  52.0%  48.0% 44.0% GWP 4 4 4 4 4 4 3 3 3 3 3 3Evaporator pressure bar 1.05 1.12 1.17 1.21 1.25 1.29 1.32 1.34 1.361.38 1.39 1.39 Condenser pressure bar 7.65 7.96 8.21 8.42 8.60 8.74 8.858.93 8.98 9.02 9.03 9.03 Pressure ratio 7.25 7.13 7.03 6.93 6.85 6.786.71 6.65 6.60 6.55 6.51 6.47 Volumetric efficiency  87.8%  88.1%  88.4% 88.7%  88.9%  89.1%  89.3%  89.5%  89.7%  89.9%  90.0%  90.1% Dischargetemperature ° C. 17.7 19.2 20.5 21.7 22.8 23.9 24.9 25.9 26.9 27.9 29.030.0 Evaporator temp glide K 1.0 1.4 1.5 1.5 1.4 1.3 1.1 1.0 0.9 0.8 0.80.8 Condenser temp glide K 1.6 1.8 1.9 1.8 1.7 1.5 1.4 1.3 1.3 1.3 1.41.4 Volumetric capacity kJ/m3 834 881 921 956 987 1012 1034 1052 10671078 1086 1091 Cooling COP 2.27 2.28 2.29 2.30 2.31 2.31 2.32 2.32 2.332.33 2.33 2.33 R744 (weight %)   8.0%   8.0%   8.0%   8.0%   8.0%   8.0%  8.0%   8.0%   8.0%  8.0%  8.0% R170 (weight %)  52.0%  56.0%  60.0% 64.0%  68.0%  70.0%  76.0%  80.0%  84.0% 88.0% 92.0% R1132a (weight %)44.00% 40.00% 36.00% 32.00% 28.00% 26.00% 20.00% 16.00% 12.00% 8.00%4.00% GWP 3 3 3 3 3 3 3 3 3 3 3 Evaporator pressure bar 1.40 1.40 1.401.40 1.39 1.39 1.38 1.37 1.36 1.36 1.35 Condenser pressure bar 9.02 8.998.96 8.92 8.87 8.82 8.76 8.70 8.64 8.58 8.51 Pressure ratio 6.45 6.426.40 6.39 6.37 6.36 6.35 6.34 6.33 6.33 6.32 Volumetric efficiency 90.2%  90.3%  90.4%  90.5%  90.6%  90.7%  90.8%  90.8%  90.9%  90.9% 91.0% Discharge temperature ° C. 31.1 32.2 33.3 34.4 35.5 36.6 37.638.7 39.7 40.7 41.7 Evaporator temp glide K 0.8 0.9 1.0 1.1 1.2 1.3 1.41.5 1.5 1.6 1.7 Condenser temp glide K 1.5 1.7 1.8 1.9 2.1 2.2 2.3 2.42.5 2.5 2.6 Volumetric capacity kJ/m3 1094 1095 1094 1092 1088 1084 10781072 1066 1059 1052 Cooling COP 2.33 2.33 2.33 2.33 2.33 2.33 2.32 2.322.32 2.31 2.31

TABLE 14 Refrigeration performance modelling data for R-1132a/R-170/CO₂ternary system with 12% by weight CO₂ R744 (weight %) 12.0% 12.0% 12.0%12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% R170 (weight %)  4.0% 8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% 44.0% R1132a(weight %) 84.0% 80.0% 76.0% 72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0%44.0% GWP 4 4 4 3 3 3 3 3 3 3 3 Evaporator pressure bar 1.08 1.15 1.201.25 1.29 1.33 1.36 1.39 1.41 1.42 1.43 Condenser pressure bar 7.91 8.228.49 8.71 8.89 9.03 9.14 9.23 9.28 9.32 9.33 Pressure ratio 7.29 7.177.06 6.96 6.87 6.79 6.72 6.66 6.60 6.55 6.51 Volumetric efficiency 87.9%88.2% 88.5% 88.8% 89.0% 89.2% 89.4% 89.6% 89.8% 89.9% 90.1% Dischargetemperature ° C. 20.2 21.6 22.9 24.0 25.1 26.1 27.1 28.1 29.0 30.0 31.0Evaporator temp glide K 1.1 1.5 1.7 1.7 1.6 1.4 1.3 1.2 1.1 1.0 1.0Condenser temp glide K 1.9 2.1 2.2 2.1 2.0 1.8 1.7 1.7 1.7 1.7 1.8Volumetric capacity kJ/m3 860 909 950 986 1017 1043 1066 1084 1099 11111119 Cooling COP 2.26 2.27 2.28 2.29 2.30 2.30 2.31 2.31 2.31 2.32 2.32R744 (weight %) 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0%12.0% 12.0% R170 (weight %) 48.0% 52.0% 56.0% 60.0% 64.0% 68.0% 70.0%76.0% 80.0% 84.0% 88.0% R1132a (weight %) 40.0% 36.0% 32.0% 28.0% 24.0%20.0% 18.0% 12.0%  8.0%  4.0%  0.0% GWP 3 3 3 3 3 3 3 3 3 3 3 Evaporatorpressure bar 1.44 1.45 1.45 1.45 1.44 1.44 1.43 1.43 1.42 1.41 1.40Condenser pressure bar 9.33 9.31 9.28 9.25 9.20 9.16 9.10 9.04 8.98 8.928.86 Pressure ratio 6.47 6.44 6.42 6.40 6.38 6.36 6.35 6.33 6.32 6.316.31 Volumetric efficiency 90.2% 90.3% 90.4% 90.5% 90.6% 90.7% 90.8%90.9% 90.9% 91.0% 91.0% Discharge temperature ° C. 32.1 33.1 34.2 35.336.4 37.5 38.5 39.6 40.6 41.6 42.6 Evaporator temp glide K 1.0 1.1 1.21.4 1.5 1.6 1.8 1.9 2.1 2.2 2.3 Condenser temp glide K 1.9 2.1 2.3 2.42.6 2.8 3.0 3.1 3.3 3.4 3.5 Volumetric capacity kJ/m3 1125 1128 11281127 1125 1122 1117 1112 1107 1100 1094 Cooling COP 2.32 2.32 2.32 2.322.32 2.32 2.32 2.31 2.31 2.31 2.31

TABLE 15 Refrigeration performance modelling data for R-1132a/R-170/CO₂ternary system with 16% by weight CO₂ R744 (weight %) 16.0% 16.0% 16.0%16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% R170 (weight %)  4.0% 8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0% 44.0% R1132a(weight %) 80.0% 76.0% 72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0% 44.0%40.0% GWP 3 3 3 3 3 3 3 3 3 3 3 Evaporator pressure bar 1.11 1.18 1.241.29 1.33 1.37 1.40 1.43 1.45 1.47 1.48 Condenser pressure bar 8.15 8.488.75 8.98 9.17 9.32 9.43 9.52 9.57 9.61 9.62 Pressure ratio 7.33 7.207.08 6.98 6.89 6.81 6.73 6.67 6.60 6.55 6.51 Volumetric efficiency 88.0%88.3% 88.6% 88.9% 89.1% 89.3% 89.5% 89.7% 89.9% 90.0% 90.2% Dischargetemperature ° C. 22.8 24.1 25.3 26.4 27.4 28.4 29.3 30.2 31.1 32.0 33.0Evaporator temp glide K 1.2 1.6 1.8 1.8 1.7 1.6 1.4 1.3 1.2 1.2 1.2Condenser temp glide K 2.1 2.3 2.4 2.3 2.2 2.1 2.0 1.9 2.0 2.0 2.2Volumetric capacity kJ/m3 886 936 978 1015 1046 1074 1097 1116 1131 11431152 Cooling COP 2.26 2.27 2.27 2.28 2.29 2.29 2.29 2.30 2.30 2.31 2.31R744 (weight %) 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0% 16.0%16.0% R170 (weight %) 48.0% 52.0% 56.0% 60.0% 64.0% 68.0% 70.0% 76.0%80.0% 84.0% R1132a (weight %) 36.0% 32.0% 28.0% 24.0% 20.0% 16.0% 12.0% 8.0%  4.0%  0.0% GWP 3 3 3 3 3 3 3 3 3 3 Evaporator pressure bar 1.491.49 1.49 1.49 1.49 1.49 1.48 1.47 1.47 1.46 Condenser pressure bar 9.629.60 9.57 9.53 9.48 9.43 9.37 9.31 9.25 9.19 Pressure ratio 6.47 6.436.41 6.38 6.36 6.35 6.33 6.32 6.30 6.29 Volumetric efficiency 90.3%90.4% 90.5% 90.6% 90.7% 90.8% 90.9% 91.0% 91.0% 91.1% Dischargetemperature ° C. 34.0 35.1 36.1 37.2 38.3 39.4 40.4 41.5 42.5 43.5Evaporator temp glide K 1.3 1.4 1.5 1.7 1.9 2.1 2.2 2.4 2.6 2.8Condenser temp glide K 2.3 2.5 2.7 3.0 3.2 3.4 3.6 3.8 4.0 4.1Volumetric capacity kJ/m3 1157 1160 1161 1160 1158 1154 1150 1145 11401134 Cooling COP 2.31 2.31 2.31 2.31 2.31 2.31 2.31 2.31 2.30 2.30

TABLE 16 Refrigeration performance modelling data forR-1132a/R-116/R-170 ternary system with 4% by weight R-1132a R170(weight %)  4.0%  8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0%44.0% 48.0% R1132a (weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% 4.0%  4.0%  4.0%  4.0%  4.0% R116 (weight %) 92.0% 88.0% 84.0% 80.0%76.0% 72.0% 68.0% 64.0% 60.0% 56.0% 52.0% 48.0% GWP 11224 10736 102499761 9273 8785 8297 7809 7321 6833 6345 5858 Evaporator pressure bar0.96 1.13 1.25 1.35 1.42 1.48 1.52 1.54 1.53 1.52 1.50 1.48 Condenserpressure bar 7.09 7.90 8.49 8.91 9.20 9.38 9.45 9.45 9.40 9.32 9.22 9.12Pressure ratio 7.36 6.97 6.76 6.62 6.48 6.35 6.22 6.15 6.13 6.13 6.146.15 Volumetric efficiency 85.4% 86.5% 87.2% 87.8% 88.3% 88.8% 89.2%89.6% 89.8% 89.9% 90.1% 90.2% Discharge temperature ° C. −6.1 −2.4 0.63.0 5.0 6.7 8.2 10.1 12.5 15.0 17.5 19.8 Evaporator temp glide K 4.4 5.55.0 3.8 2.5 1.3 0.4 0.0 0.1 0.4 0.7 1.0 Condenser temp glide K 4.8 4.73.5 2.2 1.1 0.3 0.0 0.0 0.2 0.5 0.8 1.1 Volumetric capacity kJ/m3 762898 990 1057 1112 1156 1189 1204 1203 1193 1180 1166 Cooling COP 2.402.46 2.47 2.47 2.48 2.49 2.51 2.51 2.51 2.49 2.48 2.47 R170 (weight %)52.0% 56.0% 60.0% 64.0% 68.0% 72.0% 76.0% 80.0% 84.0% 88.0% 92.0% R1132a(weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% 4.0% R116 (weight %) 44.0% 40.0% 36.0% 32.0% 28.0% 24.0% 20.0% 16.0%12.0%  8.0%  4.0% GWP 5370 4882 4394 3906 3418 2930 2442 1955 1467 979491 Evaporator pressure bar 1.46 1.44 1.43 1.41 1.39 1.36 1.34 1.32 1.301.28 1.26 Condenser pressure bar 9.02 8.91 8.81 8.70 8.60 8.49 8.39 8.288.18 8.07 7.96 Pressure ratio 6.16 6.17 6.18 6.19 6.21 6.22 6.24 6.266.28 6.30 6.32 Volumetric efficiency 90.3% 90.4% 90.5% 90.5% 90.6% 90.7%90.7% 90.8% 90.8% 90.8% 90.9% Discharge temperature ° C. 21.9 23.9 25.827.5 29.2 30.8 32.3 33.7 35.0 36.3 37.5 Evaporator temp glide K 1.2 1.41.5 1.6 1.6 1.5 1.3 1.1 0.9 0.6 0.4 Condenser temp glide K 1.3 1.5 1.61.7 1.7 1.6 1.5 1.3 1.1 0.8 0.5 Volumetric capacity kJ/m3 1152 1137 11221107 1091 1075 1058 1041 1023 1006 989 Cooling COP 2.46 2.45 2.43 2.422.41 2.40 2.39 2.37 2.36 2.35 2.34

TABLE 17 Refrigeration performance modelling data forR-1132a/R-116/R-170 ternary system with 8% by weight R-1132a R170(weight %)  4.0%  8.0% 12.0% 16.0% 20.0% 24.0% 28.0% 32.0% 36.0% 40.0%44.0% R1132a (weight%)  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% 8.0%  8.0%  8.0% R116 (weight %) 88.0% 84.0% 80.0% 76.0% 72.0% 68.0%64.0% 60.0% 56.0% 52.0% 48.0% GWP 10736 10249 9761 9273 8785 8297 78097321 6833 6346 5858 Evaporator pressure bar 1.01 1.16 1.28 1.37 1.431.49 1.52 1.53 1.52 1.51 1.49 Condenser pressure bar 7.31 8.07 8.61 8.999.25 9.40 9.45 9.43 9.37 9.29 9.19 Pressure ratio 7.27 6.93 6.74 6.596.45 6.32 6.21 6.16 6.15 6.15 6.16 Volumetric efficiency 85.7% 86.7%87.4% 87.9% 88.5% 88.9% 89.3% 89.6% 89.8% 89.9% 90.1% Dischargetemperature ° C. −5.2 −1.7 1.1 3.4 5.3 7.0 8.7 10.8 13.2 15.7 18.1Evaporator temp glide K 4.2 4.9 4.3 3.1 1.9 0.9 0.2 0.0 0.2 0.5 0.8Condenser temp glide K 4.3 4.0 2.9 1.7 0.8 0.2 0.0 0.1 0.3 0.6 0.9Volumetric capacity kJ/m3 782 908 996 1062 1115 1157 1185 1196 1192 11831171 Cooling COP 2.37 2.42 2.44 2.45 2.46 2.48 2.49 2.50 2.49 2.48 2.47R170 (weight %) 48.0% 52.0% 56.0% 60.0% 64.0% 68.0% 72.0% 76.0% 80.0%84.0% 88.0% R1132a (weight %)  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% 8.0%  8.0%  8.0%  8.0% R116 (weight %) 44.0% 40.0% 36.0% 32.0% 28.0%24.0% 20.0% 16.0% 12.0%  8.0%  4.0% GWP 5370 4882 4394 3906 3418 29302442 1955 1467 979 491 Evaporator pressure bar 1.47 1.45 1.44 1.42 1.401.37 1.35 1.33 1.31 1.29 1.27 Condenser pressure bar 9.09 8.99 8.88 8.778.67 8.56 8.46 8.35 8.24 8.14 8.03 Pressure ratio 6.17 6.18 6.19 6.206.21 6.23 6.25 6.26 6.29 6.31 6.32 Volumetric efficiency 90.2% 90.3%90.4% 90.5% 90.5% 90.6% 90.6% 90.7% 90.7% 90.8% 90.8% Dischargetemperature ° C. 20.3 22.4 24.3 26.2 27.9 29.5 31.1 32.6 33.9 35.2 36.5Evaporator temp glide K 1.0 1.2 1.4 1.4 1.4 1.4 1.3 1.1 0.9 0.6 0.4Condenser temp glide K 1.1 1.3 1.4 1.5 1.5 1.5 1.4 1.3 1.1 0.8 0.5Volumetric capacity kJ/m3 1157 1143 1129 1114 1098 1082 1065 1048 10311014 997 Cooling COP 2.46 2.45 2.44 2.42 2.41 2.40 2.39 2.38 2.36 2.352.34

TABLE 18 Refrigeration performance modelling data forR-1132a/R-116/R-170 ternary system with 12-20% by weight R-1132a R170(weight %)  4.0%  8.0% 12.0% 16.0% 20.0% 24.0% 28.0%  4.0%  8.0% 12.0%16.0% R1132a (weight %) 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 16.0%16.0% 16.0% 16.0% R116 (weight %) 84.0% 80.0% 76.0% 72.0% 68.0% 64.0%60.0% 80.0% 76.0% 72.0% 68.0% GWP 10249 9761 9273 8785 8297 7809 73219761 9273 8785 8297 Evaporator pressure bar 1.04 1.19 1.30 1.38 1.441.49 1.52 1.07 1.21 1.31 1.39 Condenser pressure bar 7.49 8.20 8.70 9.059.27 9.39 9.43 7.65 8.30 8.76 9.08 Pressure ratio 7.20 6.90 6.70 6.566.42 6.30 6.21 7.13 6.86 6.67 6.53 Volumetric efficiency 86.0% 86.9%87.5% 88.1% 88.6% 89.0% 89.4% 86.2% 87.1% 87.7% 88.2% Dischargetemperature ° C. −4.4 −1.1 1.6 3.8 5.6 7.4 9.3 −3.7 −0.5 2.0 4.2Evaporator temp glide K 3.9 4.3 3.6 2.5 1.5 0.6 0.1 3.4 3.6 3.0 2.0Condenser temp glide K 3.7 3.3 2.3 1.3 0.5 0.1 0.0 3.1 2.7 1.8 1.0Volumetric capacity kJ/m3 798 916 1001 1065 1117 1155 1178 811 923 10041067 Cooling COP 2.34 2.39 2.42 2.43 2.45 2.47 2.48 2.31 2.37 2.40 2.42R170 (weight %) 20.0% 24.0% 28.0%  4.0%  8.0% 12.0% 16.0% 20.0% 24.0%28.0% R1132a (weight %) 16.0% 16.0% 16.0% 20.0% 20.0% 20.0% 20.0% 20.0%20.0% 20.0% R116 (weight %) 64.0% 60.0% 56.0% 76.0% 72.0% 68.0% 64.0%60.0% 56.0% 52.0% GWP 7809 7321 6833 9273 8785 8297 7809 7321 6834 6346Evaporator pressure bar 1.45 1.49 1.51 1.10 1.23 1.32 1.40 1.45 1.481.50 Condenser pressure bar 9.27 9.37 9.39 7.77 8.38 8.80 9.08 9.25 9.339.34 Pressure ratio 6.40 6.29 6.22 7.07 6.82 6.65 6.50 6.38 6.29 6.24Volumetric efficiency 88.7% 89.1% 89.4% 86.5% 87.2% 87.8% 88.3% 88.8%89.1% 89.4% Discharge temperature ° C. 6.0 7.9 9.9 −3.1 0.0 2.5 4.6 6.58.5 10.7 Evaporator temp glide K 1.1 0.4 0.1 2.9 3.0 2.4 1.6 0.8 0.3 0.2Condenser temp glide K 0.4 0.1 0.1 2.5 2.2 1.4 0.8 0.3 0.1 0.1Volumetric capacity kJ/m3 1115 1150 1168 822 928 1007 1067 1111 11411156 Cooling COP 2.44 2.46 2.47 2.29 2.35 2.38 2.41 2.43 2.45 2.45

TABLE 19 Refrigeration performance modelling data forR-1132a/R-116/R-170 ternary system with 30-60% by weight R1132a R170(weight %)  4.0%  8.0% 12.0% 16.0% 20.0% 24.0% 28.0%  4.0%  8.0% 12.0%16.0% R1132a (weight %)   30%   30%   30%   30%   30%   30%   30%   40%  40%   40%   40% R116 (weight %) 66.0% 62.0% 58.0% 54.0% 50.0% 46.0%42.0% 56.0% 52.0% 48.0% 44.0% GWP 8053 7565 7078 6590 6102 5614 51266834 6346 5858 5370 Evaporator pressure bar 1.14 1.25 1.33 1.39 1.431.45 1.45 1.16 1.25 1.31 1.36 Condenser pressure bar 7.96 8.46 8.79 9.019.13 9.18 9.17 7.99 8.40 8.67 8.84 Pressure ratio 6.96 6.75 6.60 6.486.40 6.34 6.31 6.89 6.73 6.61 6.52 Volumetric efficiency 86.9% 87.6%88.1% 88.6% 88.9% 89.2% 89.4% 87.3% 87.8% 88.3% 88.6% Dischargetemperature ° C. −1.5 1.4 3.8 6.0 8.2 10.5 12.7 0.3 3.1 5.7 8.0Evaporator temp glide K 1.7 1.8 1.5 1.0 0.6 0.5 0.4 1.0 1.2 1.1 1.0Condenser temp glide K 1.4 1.3 0.9 0.5 0.3 0.3 0.3 0.9 1.0 0.8 0.6Volumetric capacity kJ/m³ 842 935 1004 1055 1090 1111 1122 851 930 9891030 Cooling COP 2.26 2.32 2.36 2.38 2.40 2.41 2.42 2.25 2.30 2.34 2.36R170 (weight %) 20.0% 24.0% 28.0%  4.0%  8.0% 12.0% 16.0% 20.0% 24.0%28.0% R1132a (weight %)   40%   40%   40% 60.0% 60.0% 60.0% 60.0% 60.0%60.0% 60.0% R116 (weight %) 40.0% 36.0% 32.0% 36.0% 32.0% 28.0% 24.0%20.0% 16.0% 12.0% GWP 4882 4394 3906 4395 3907 3419 2931 2443 1955 1467Evaporator pressure bar 1.38 1.40 1.40 1.12 1.19 1.23 1.26 1.28 1.291.30 Condenser pressure bar 8.94 8.98 8.97 7.79 8.08 8.28 8.41 8.48 8.518.51 Pressure ratio 6.46 6.42 6.39 6.92 6.81 6.73 6.66 6.62 6.58 6.56Volumetric efficiency 88.9% 89.2% 89.4% 87.6% 88.0% 88.4% 88.7% 88.9%89.1% 89.3% Discharge temperature ° C. 10.3 12.6 14.7 4.9 7.6 10.1 12.414.5 16.5 18.4 Evaporator temp glide K 0.8 0.7 0.7 0.9 1.3 1.4 1.3 1.21.0 0.8 Condenser temp glide K 0.5 0.5 0.5 0.9 1.1 1.1 1.0 0.9 0.7 0.6Volumetric capacity kJ/m³ 1058 1076 1085 837 895 938 968 990 1004 1012Cooling COP 2.38 2.39 2.39 2.25 2.29 2.32 2.33 2.35 2.35 2.36

TABLE 20 Refrigeration performance modelling data forR-1132a/R-116/R-170/R-744 quaternary system with 4-12% by weight R-744R170 (weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  8.0% 8.0%  8.0% R744 (weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% 4.0%  8.0%  8.0%  8.0% R1132a (weight %) 20.0% 30.0% 40.0% 50.0% 60.0%70.0% 80.0% 90.0% 20.0% 30.0% 40.0% R116 (weight %) 76.0% 66.0% 56.0%46.0% 36.0% 26.0% 16.0%  6.0% 72.0% 62.0% 52.0% GWP 9273 8053 6834 56144395 3175 1955 736 8785 7566 6346 Evaporator pressure bar 1.19 1.22 1.221.20 1.16 1.13 1.09 1.05 1.39 1.38 1.35 Condenser pressure bar 8.45 8.528.46 8.33 8.14 7.93 7.72 7.49 9.50 9.40 9.21 Pressure ratio 7.08 6.996.95 6.95 6.99 7.04 7.10 7.17 6.84 6.81 6.82 Volumetric efficiency 86.7%87.1% 87.4% 87.6% 87.7% 87.7% 87.8% 87.8% 87.6% 87.8% 88.0% Dischargetemperature ° C. 0.6 2.0 3.6 5.7 7.9 10.1 12.1 13.9 6.1 7.3 8.9Evaporator temp glide K 3.5 2.1 1.4 1.2 1.2 1.3 1.2 1.0 3.6 2.3 1.8Condenser temp glide K 3.8 2.4 1.8 1.6 1.6 1.6 1.5 1.3 3.7 2.6 2.2Volumetric capacity kJ/m3 904 909 905 893 875 856 837 816 1064 1046 1021Cooling COP 2.31 2.27 2.26 2.25 2.25 2.25 2.26 2.27 2.35 2.32 2.30 R170(weight %)  8.0%  8.0%  8.0%  8.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0%12.0% R744 (weight %)  8.0%  8.0%  8.0%  8.0% 12.0% 12.0% 12.0% 12.0%12.0% 12.0% 12.0% R1132a (weight %) 50.0% 60.0% 70.0% 80.0% 20.0% 30.0%40.0% 50.0% 60.0% 70.0% 80.0% R116 (weight %) 42.0% 32.0% 22.0% 12.0%68.0% 58.0% 48.0% 38.0% 28.0% 18.0%  8.0% GWP 5126 3907 2687 1468 82977078 5858 4638 3419 2199 980 Evaporator pressure bar 1.31 1.26 1.21 1.161.53 1.50 1.44 1.39 1.33 1.27 1.22 Condenser pressure bar 8.97 8.71 8.458.18 10.24 10.01 9.73 9.43 9.13 8.83 8.55 Pressure ratio 6.87 6.93 6.997.06 6.68 6.69 6.74 6.81 6.88 6.95 7.02 Volumetric efficiency 88.1%88.1% 88.1% 88.1% 88.3% 88.4% 88.5% 88.5% 88.5% 88.4% 88.4% Dischargetemperature ° C. 10.9 12.9 14.9 16.6 10.4 11.7 13.5 15.4 17.2 18.9 20.5Evaporator temp glide K 1.7 1.8 1.8 1.6 3.0 2.1 1.9 2.0 2.0 2.0 1.8Condenser temp glide K 2.2 2.2 2.2 2.1 3.1 2.5 2.3 2.4 2.4 2.4 2.3Volumetric capacity kJ/m3 991 961 931 903 1180 1144 1103 1062 1024 988954 Cooling COP 2.29 2.28 2.28 2.28 2.37 2.34 2.32 2.30 2.29 2.29 2.28

TABLE 21 Refrigeration performance modelling data forR-1132a/R-116/R-170/R-744 quaternary system with 8-24% by weight R-744R170 (weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  8.0% 8.0%  8.0% R744 (weight %)  8.0%  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% 8.0% 16.0% 16.0% 16.0% R1132a (weight %) 20.0% 30.0% 40.0% 50.0% 60.0%70.0% 80.0% 90.0% 20.0% 30.0% 40.0% R116 (weight %) 76.0% 66.0% 56.0%46.0% 36.0% 26.0% 16.0%  6.0% 72.0% 62.0% 52.0% GWP 9273 8053 6834 56144395 3175 1955 736 8785 7566 6346 Evaporator pressure bar 1.27 1.28 1.271.24 1.20 1.16 1.11 1.07 1.49 1.46 1.42 Condenser pressure bar 8.97 8.968.84 8.66 8.44 8.21 7.97 7.73 10.22 10.02 9.75 Pressure ratio 7.07 7.016.98 7.00 7.05 7.10 7.15 7.22 6.85 6.85 6.89 Volumetric efficiency 86.9%87.2% 87.5% 87.6% 87.7% 87.8% 87.8% 87.8% 87.9% 88.1% 88.2% Dischargetemperature ° C. 3.7 4.9 6.5 8.5 10.6 12.6 14.5 16.2 10.9 12.1 13.7Evaporator temp glide K 3.6 2.2 1.5 1.4 1.4 1.4 1.4 1.1 3.2 2.3 2.0Condenser temp glide K 4.2 2.8 2.2 2.0 2.0 2.0 1.9 1.7 3.6 2.8 2.5Volumetric capacity kJ/m3 970 963 950 930 908 885 863 840 1152 1120 1082Cooling COP 2.32 2.28 2.26 2.25 2.25 2.25 2.26 2.26 2.35 2.32 2.29 R170(weight %)  8.0%  8.0%  8.0%  8.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0%12.0% R744 (weight %) 16.0% 16.0% 16.0% 16.0% 24.0% 24.0% 24.0% 24.0%24.0% 24.0% 24.0% R1132a (weight %) 50.0% 60.0% 70.0% 80.0% 20.0% 30.0%40.0% 50.0% 60.0% 70.0% 80.0% R116 (weight %) 42.0% 32.0% 22.0% 12.0%68.0% 58.0% 48.0% 38.0% 28.0% 18.0%  8.0% GWP 5126 3907 2687 1468 82977078 5858 4639 3419 2199 980 Evaporator pressure bar 1.36 1.31 1.25 1.201.64 1.58 1.51 1.45 1.39 1.33 1.27 Condenser pressure bar 9.46 9.16 8.878.59 11.02 10.70 10.35 10.01 9.68 9.36 9.05 Pressure ratio 6.95 7.017.07 7.14 6.72 6.77 6.84 6.91 6.98 7.05 7.11 Volumetric efficiency 88.2%88.2% 88.2% 88.2% 88.6% 88.6% 88.6% 88.6% 88.6% 88.6% 88.5% Dischargetemperature ° C. 15.6 17.4 19.1 20.7 16.4 17.9 19.6 21.3 22.9 24.3 25.7Evaporator temp glide K 1.9 2.0 1.9 1.8 2.4 2.1 2.1 2.1 2.2 2.1 2.0Condenser temp glide K 2.5 2.6 2.6 2.5 2.7 2.4 2.5 2.6 2.7 2.7 2.6Volumetric capacity kJ/m3 1045 1009 976 944 1270 1219 1168 1122 10791040 1004 Cooling COP 2.28 2.27 2.27 2.27 2.35 2.32 2.30 2.28 2.27 2.272.26

TABLE 22 Refrigeration performance modelling data forR-1132a/R-116/R-170/R-744 quaternary system with 12-36% b/w R-744 R170(weight %)  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  8.0%  8.0% 8.0% R744 (weight %) 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 12.0%24.0% 24.0% 24.0% R1132a (weight %) 20.0% 30.0% 40.0% 50.0% 60.0% 70.0%80.0% 90.0% 20.0% 30.0% 40.0% R116 (weight %) 76.0% 66.0% 56.0% 46.0%36.0% 26.0% 16.0%  6.0% 72.0% 62.0% 52.0% GWP 9273 8053 6834 5614 43953175 1955 736 8785 7566 6346 Evaporator pressure bar 1.33 1.33 1.31 1.271.23 1.18 1.14 1.09 1.56 1.51 1.46 Condenser pressure bar 9.40 9.32 9.168.94 8.69 8.44 8.19 7.94 10.71 10.45 10.14 Pressure ratio 7.06 7.02 7.027.05 7.09 7.14 7.20 7.26 6.87 6.90 6.95 Volumetric efficiency 87.1%87.4% 87.6% 87.7% 87.8% 87.8% 87.8% 87.8% 88.2% 88.3% 88.3% Dischargetemperature ° C. 6.4 7.6 9.2 11.1 13.1 15.0 16.7 18.3 14.9 16.3 17.9Evaporator temp glide K 3.4 2.2 1.6 1.5 1.5 1.5 1.4 1.2 2.6 2.1 2.0Condenser temp glide K 4.1 3.0 2.4 2.3 2.2 2.2 2.1 1.9 3.1 2.6 2.5Volumetric capacity kJ/m3 1023 1008 988 962 936 911 886 861 1211 11691125 Cooling COP 2.32 2.28 2.26 2.25 2.25 2.25 2.25 2.26 2.34 2.31 2.29R170 (weight %)  8.0%  8.0%  8.0%  8.0% 12.0% 12.0% 12.0% 12.0% 12.0%12.0% 12.0% R744 (weight %) 24.0% 24.0% 24.0% 24.0% 36.0% 36.0% 36.0%36.0% 36.0% 36.0% 36.0% R1132a (weight %) 50.0% 60.0% 70.0% 80.0% 20.0%30.0% 40.0% 50.0% 60.0% 70.0% 80.0% R116 (weight %) 42.0% 32.0% 22.0%12.0% 68.0% 58.0% 48.0% 38.0% 28.0% 18.0%  8.0% GWP 5126 3907 2687 14688298 7078 5858 4639 3419 2200 980 Evaporator pressure bar 1.40 1.34 1.291.24 1.69 1.62 1.55 1.48 1.42 1.36 1.31 Condenser pressure bar 9.82 9.519.20 8.91 11.46 11.10 10.74 10.38 10.04 9.72 9.41 Pressure ratio 7.027.08 7.13 7.19 6.79 6.86 6.93 7.00 7.06 7.12 7.18 Volumetric efficiency88.3% 88.3% 88.3% 88.3% 88.8% 88.8% 88.8% 88.7% 88.7% 88.7% 88.6%Discharge temperature ° C. 19.6 21.3 22.8 24.2 21.7 23.3 24.8 26.3 27.728.9 30.1 Evaporator temp glide K 2.0 2.0 2.0 1.9 2.0 2.0 2.1 2.2 2.22.1 2.0 Condenser temp glide K 2.6 2.7 2.7 2.6 2.1 2.1 2.3 2.5 2.6 2.72.6 Volumetric capacity kJ/m3 1083 1045 1010 977 1316 1259 1206 11591116 1077 1040 Cooling COP 2.27 2.26 2.26 2.26 2.33 2.30 2.28 2.27 2.262.25 2.25

Flammability Data

The flammability behaviour of binary mixtures of R1132a withnon-flammable R116 or R744 (carbon dioxide) was studied using a 12 literglass flask apparatus, conforming to the apparatus and test methoddescribed in ASHRAE Standard 34 for evaluation of flammability ofrefrigerants. Binary mixtures of varying composition were tested usingthe Standard 34 test method at 60° C. with a constant humidity(corresponding to 50% relative humidity at 25° C.) to determine themaximum quantity of R-1132a that could be added to each non-flammablecomponent without resulting in a flammable mixture.

It was found that the maximum quantity of R-1132a that could be added toR-116 without making the mixture flammable was 48% by volume, whichcorresponds to a composition of 30.5% by weight R-1132a, 69.5% by weightR-116. It was further determined that the maximum quantity of R-1132athat could be added to R-744 without generating a flammable mixture was15% by volume.

These flammability data are depicted pictorially in FIG. 6, showing atriangular composition diagram for ternary mixtures of R-744, R-1132aand R-116, with the units of composition being volume fraction. A dashedline is shown connecting the non-flammable binary compositions havingthe maximum quantity of R-1132a. Ternary compositions lying above and tothe right of this line are anticipated to be non-flammable and arepreferred compositions of the invention.

Performance Data—Binary R-1132a/R-116 Blends

The performance of selected binary compositions of R-1132a/R-116 wasstudied using a biomedical storage freezer appliance. This appliance wasa Panasonic model MDF-U76VC freezer, comprising a cascade refrigerationsystem with a lower temperature stage operating on R-508B and an uppertemperature stage rejecting heat to external ambient air using R-404Arefrigerant. Its performance specification for the achieved internalstorage compartment air temperature is −86° C. or lower when operated inan ambient air temperature of 30° C. The test was carried out as adrop-in test in which the R-508B refrigerant in the low temperaturestage was replaced by binary compositions of the invention and thesystem was operated in a climate room to guarantee an ambienttemperature of 30° C. The storage compartment air temperature, motorpower consumption, refrigeration compressor operating temperature andpressure and refrigerant evaporating and condensing temperatures wereall recorded. A reference test was carried out with R-508B refrigerantto provide comparative data. A further reference test was carried outusing pure R-1132a in the lower stage to provide further comparativedata.

The results recorded are shown in the following table. It was found thatalthough R1132a alone could not meet the internal air temperaturetarget, addition of R116 improved the performance of the refrigerant.This was demonstrated by the achieved cabinet air temperatures. Thepresence of the R1132a/R116 azeotrope was demonstrated by the airtemperature going through a minimum as the azeotropic composition of ca.50% w/w R1132a was approached. A composition of 51.1% R1132a/49.9% R116was found to deliver an acceptable air temperature compared to thatachieved with R-508B but at a lower compressor exit temperature. Thelatter is desirable to protect the compressor and avoid thermaldegradation of its lubricating oil.

TABLE 23 Refrigeration performance data for selected R-1132a/R-116blends Compressor exit Cabinet air R-116 content temperature temperaturePower (% w/w) (° C.) (° C.) (W) 0 83.5 −85.3 1132 16.9 83.6 −87.7 114529.8 83.7 −88.4 1151 35.7 84.1 −88.6 1157 40.4 84.1 −88.7 1162 45.3 84.7−88.5 1189 49.7 84.7 −88.5 1189 R508B comparison 85.4 −89.5 1158

Performance Data—Ternary R-744/R-1132a/R-116 Blends

In the same equipment as used for binary composition testing were testedseveral ternary compositions of R-744/R-1132a/R-116 at the sameoperating conditions. These were selected as non-flammable compositionson the basis of the flammability data reported above. Selected resultsare reproduced below.

TABLE 24 Refrigeration performance data for selected R-1132a/R-116/CO₂blends Ambient Temperature 30° C. R508B Mixture A Mixture B Mixture CMixture D R-1123 (% w/w) 33.6% 31.1% 30.0% 29.1% R-116 (% w/w) 66.4%61.5% 59.4% 57.5% R-744 (% w/w) 0.0% 7.4% 10.6% 13.4% Compressor exittemperature (° C.) 81.6 80.2 80.8 82.0 81.1 Cabinet air temperature (°C.) −88.2 −83.4 −87.2 −88.3 −89.2 Power Input(W) 1070 1040 1060 10801080

The ternary compositions delivered performance close to R508B. It wasfound that at the highest concentration of R-744 tested (13.4% w/w)slight instability in operation was observed, attributed to dry iceformation in the expansion device. Since this is an undesirable feature,it is concluded that for compositions where the mass ratio of R1132a toR116 is selected to ensure that this mixture is non-flammable, the R744content is preferably less than about 13% w/w of the total.

Next were tested ternary compositions wherein the R-1132a/R-116composition was close to the azeotropic composition and which areexpected to be mildly flammable. Results from selected tests are shownin the table below.

TABLE 25 Refrigeration performance data for further selectedR-1132a/R-116/CO₂ blends Ambient Mix- Temperature Mixture MixtureMixture Mixture ture 30° C. R508B E F G H J R-1132a (% w/w) 50.2% 45.4%44.1% 42.7% 41.5% R-116 (% w/w) 49.8% 45.1% 43.8% 42.4% 41.3% R-744 (%w/w)  0.0%  9.6% 12.2% 14.9% 17.2% Compressor exit 81.6 83.2 81.4 82.182.1 82.7 temperature (° C.) Cabinet air −88.2 −87.60 −90.0 −90.1 −90.4−90.3 temperature (° C.) Power Input (W) 1070 1080 1100 1100 1100 1100

It is believed that at lower concentrations of R-116 a further increasein R-744 content may be achieved without formation of dry ice, and thuscertain preferred ternary R-744/R-1132a/R-116 compositions are thosewherein the refrigeration performance can deliver a final airtemperature within 3K of that achievable with R-508B without theformation of dry ice in the systems' expansion device or evaporatorinlet pipe.

To investigate the potential maximum amount of R-744 that could be addeda study was carried out by adding progressively increasing quantities ofR744 to mixtures of R1132a and R116 in a constant volume stirred vesselat a temperature of −66° C. (selected as being below the triple point ofR-744) and measuring the vapour pressure of the resulting ternarymixtures after mixing and equilibration of the system. Two binarycomposition ratios of R-1132a/R-116 were used (28 mol % and 75 mol %R1132a). It was found that with both these tests that the maximumquantity of R-744 that could be added before the vapour pressure nolonger increased on further addition of R-744, which indicated formationof solid phase R-744, was about 0.5 mol fraction in the ternary mixture.Thus additionally preferred ternary compositions are those wherein themol fraction of R-744 in the ternary composition is less than 0.5 withmore preferred compositional limits as explained above.

The invention is defined by the following claims.

The invention claimed is:
 1. A heat transfer composition comprising from20 to 99% by weight 1,1-difluoroethene (R-1132a); from 1 to 80% byweight ethane (R-170); a lubricant selected from: mineral oil, siliconeoil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkyleneglycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinylethers (PVEs), poly (alpha-olefins), and combinations thereof; and,optionally carbon dioxide (R-744).
 2. A composition according to claim1, further comprising hexafluoroethane (R-116).
 3. A compositionaccording to claim 1, wherein the composition is selected from the groupconsisting of: 1 to 50% by weight ethane and from 50 to 99% by weightR-1132a; 1 to 25% by weight ethane and from 75 to 99% by weight R-1132a;R-1132a, ethane and up to 70% by weight CO₂; 2 to 98% by weight ofR-1132a, from 2 to 98% by weight of ethane, and from 2 to 60% by weightCO₂; 4 to 96% by weight of R-1132a, from 4 to 96% by weight of ethaneand from 4 to 50% by weight CO₂; and R-1132a, ethane, and from 6 to 40%by weight CO₂.
 4. A composition according to claim 1, further comprisingpentafluoroethane (R-125).
 5. A composition according to claim 1,further comprising a hydrocarbon, wherein the hydrocarbon is in additionto any ethane present in the composition.
 6. A composition according toclaim 1, wherein the composition is less flammable than R-1132a alone.7. A composition according to claim 6, wherein the composition has: a. ahigher flammable limit; b. a higher ignition energy; and/or c. a lowerflame velocity compared to R-1132a alone.
 8. A composition according toclaim 1 that is non-flammable.
 9. A composition according to claim 8,wherein the composition is non-flammable at ambient temperature, saidambient temperature including at least 60° C.
 10. A compositionaccording to claim 1 that has a temperature glide in an evaporator orcondenser of less than about 10K.
 11. A composition according to claim 1that has a critical temperature of greater than 0° C.
 12. A compositionaccording to claim 1 that has a volumetric refrigeration capacity of atleast 90% of that of R-508B at comparable cycle conditions.
 13. Acomposition according to claim 1 that has a compressor dischargetemperature that is within 15K of that of R-508B at comparable cycleconditions.
 14. A composition according to claim 1, further comprising acomponent selected from a stabiliser, a flame retardant, and anycombination thereof.
 15. A composition according to claim 5, wherein thestabiliser is selected from: diene-based compounds, phosphates, phenolcompounds and epoxides, and any mixtures thereof.
 16. A compositionaccording to claim 5, wherein the flame retardant is selected from:tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminium trihydrate, polyvinyl chloride, a fluorinatediodocarbon, a fluorinated bromocarbon, trifluoro iodomethane,perfluoroalkyl amines, bromo-fluoroalkyl amines, and any mixturesthereof.
 17. A heat transfer device containing a composition as definedclaim
 1. 18. A heat transfer device according to claim 10, wherein theheat transfer device comprises a component selected from the groupconsisting of one or more of: a refrigeration device; an ultra-lowtemperature refrigeration system; and a cascade system.
 19. A method forcooling an article, comprising condensing a composition defined in claim1 and thereafter evaporating the composition in a vicinity of thearticle to be cooled.
 20. A method for heating an article, comprisingcondensing a composition as defined in claim 1 in a vicinity of thearticle to be heated and thereafter evaporating the composition.
 21. Amechanical power generation device containing a composition as definedin claim
 1. 22. A mechanical power generating device according to claim21 that is adapted to use a Rankine Cycle or modification thereof togenerate work from heat.
 23. A method of retrofitting a heat transferdevice, comprising the steps of removing an existing heat transfercomposition, and introducing a composition as defined in claim
 1. 24. Amethod of claim 23, wherein the heat transfer device is a refrigerationdevice.
 25. A method according to claim 24 wherein the heat transferdevice is an ultra-low temperature refrigeration system.
 26. The methodof claim 23 carried out on a product from a field selected from:air-conditioning, refrigeration and heat transfer.
 27. A method forreducing environmental impact arising from operation of a productcomprising an existing compound or composition, the method comprisingreplacing at least partially the existing compound or composition with acomposition as defined in claim
 1. 28. The method according to claim 27,wherein the product is selected from: a heat transfer device and amechanical power generation device.
 29. The method according to claim27, wherein the existing compound or composition is a heat transfercomposition.
 30. The method according to claim 29, wherein the heattransfer composition is a refrigerant selected from R-508A, R-508B, R23and R13B1.
 31. A method for generating greenhouse gas emission credit,comprising (i) replacing an existing compound or composition with acomposition as defined in claim 1, wherein the composition as defined inclaim 1 has a lower GWP than the existing compound or composition; and(ii) obtaining greenhouse gas emission credit for said replacing step.32. The method of claim 31, wherein the method results in a lower TotalEquivalent Warming Impact, and/or a lower Life-Cycle Carbon Productionthan is attained by use of the existing compound or composition.
 33. Themethod according to claim 28, wherein the product is a heat transferdevice.
 34. The method according to claim 33, wherein the product is anultra-low temperature refrigeration system.